Fungicidal Pyrimidine Compounds

ABSTRACT

The present invention relates to fungicidal pyrimidine compounds I, to their use and to methods for combating phytopathogenic fungi. The present invention also relates to seeds treated with at least one such compound. Furthermore the invention relates to processes for preparing compounds of formula I.

The present invention relates to fungicidal pyrimidine compounds, totheir use and to methods for combating phytopathogenic fungi. Thepresent invention also relates to seeds treated with at least one suchcompound. Furthermore the invention relates to processes for preparingcompounds of formula I.

WO 98/03272 A1 describes a process for the preparation of4-amino-5-chloro-6-(1-fluoroethyl)pyrimidine compounds, which are pestcontrolling agents for agricultural and horticultural use. WO 97/28133A1 discloses acylated 4-amino and 4-hydrazinopyrimidines and their useas pesticides. WO 95/18795 A1 relates to N-(4-pyrimidinyl)amidepesticides and EP 665225 A1 relates to 4-phenethylamino pyrimidinederivatives useful for chemical control of noxious organisms.

The compounds according to the present invention differ from thosedescribed in the abovementioned publications in that the pyrimidine ringcarries a halogen substituent in 6-position and/or the specific linker Xas defined herein.

EP 264217 A2 generally discloses certain aryl alkyl amino pyrimidinederivatives inter alia with fungicidal activity of formula:

EP 264217 A2 does not mention the specific combination of a halogensubstituent in 6-position of the pyrimidine ring and the specificethylene linker unit —X—CR¹R² as defined herein together with aheteroaryloxy substitution of the phenyl ring.

In many cases, in particular at low application rates, the fungicidalactivity of known fungicidal compounds is unsatisfactory. Based on this,it was an object of the present invention to provide compounds havingimproved activity and/or a broader activity spectrum againstphytopathogenic fungi. This objective is achieved by the use ofsubstituted pyrimidine compounds of formula I having good fungicidalactivity against phytopathogenic harmful fungi.

Accordingly, the present invention relates to compounds of the formula I

wherein:

-   R^(a2), R^(a5) independently of each other, are hydrogen, halogen,    CN, NO₂, OH, SH, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,    C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio,    C₁-C₄-alkylsulfinyl, C₁-C₄-haloalkylsulfinyl, C₁-C₄-alkylsulfonyl,    C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,    C₁-C₄-alkoxy-C₁-C₄-alkoxy, C₂-C₄-alkenyl, C₂-C₄-alkynyl,    C₂-C₄-haloalkenyl, C₂-C₄-haloalkynyl, C₃-C₈-cycloalkyl,    C₃-C₈-cycloalkyloxy, C₃-C₈-cycloalkyl-C₁-C₄-alkyl, NR^(A)R^(B),    C(═O)R′, C(═NOR″)R′″ or —C(═NH)—O—R′″;    -   R^(A), R^(B) independently of each other are hydrogen,        C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, phenyl, benzyl,        C₃-C₈-cycloalkyl, C₃-C₈-cycloalkenyl or —C(═O)—R′;    -   R′ is hydrogen, OH, NH₂, C₁-C₄-alkyl, C₁-C₄-haloalkyl,        C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,        C₁-C₄-alkylamino or di(C₁-C₄-alkyl)amino;    -   R″ is hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl,        C₂-C₄-alkynyl or C₁-C₄-alkoxy-C₁-C₄-alkyl;    -   R′″ is hydrogen or C₁-C₄-alkyl;-   R^(a6) is halogen;-   R is hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,    C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl,    C₁-C₄-haloalkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl,    C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, CN, CH₂CN, NR^(A)R^(B) or    CH₂—O—C(═O)R′;-   R¹, R² independently of each other are hydrogen, halogen, CN, OH,    C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,    C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl,    C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyl, C₂-C₄-haloalkynyl,    C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyl-C₁-C₄-alkyl, C₃-C₈-cycloalkyloxy,    NR^(A)R^(B), C(═O)R′, C(═NOR″)R′″, —C(═NH)—O—R′″ or benzyl wherein    the phenyl moiety of benzyl is unsubstituted or carries 1, 2, 3, 4,    or 5 substituents selected from the group consisting of CN, halogen,    C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,    (C₁-C₄-alkoxy)carbonyl and di(C₁-C₄-alkyl)aminocarbonyl, or    -   two radicals R¹ and R² that are bound to the same carbon atom        form together with said carbon atom a saturated or partially        unsaturated 3-, 4-, 5-, 6-, or 7-membered carbocycle or a        saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered        heterocycle, wherein the ring member atoms of the abovementioned        heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms        selected from the group of N, O and S, and wherein the        abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4        substituents selected from halogen, CN, OH, SH, C₁-C₄-alkyl,        C₁-C₄-alkoxy or C₁-C₄-alkylthio; and one or two CH₂ groups of        the abovementioned cycles may be respectively replaced by one or        two C(═O) or C(═S) groups;-   X is a divalent group selected from —CR³R⁴—, —C(═NR^(D))- and    —C(═NOR^(D))—, wherein    -   R^(D) is hydrogen or C₁-C₄-alkyl, and wherein    -   R³ and R⁴ independently of each other are hydrogen, CN,        C₁-C₄-hydroxyalkyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,        C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl,        C₁-C₄-haloalkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl,        C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, C₃-C₈-cycloalkyl,        C₃-C₈-cycloalkyl-C₁-C₄-alkyl, C₃-C₈-cycloalkyloxy, NR^(A)R^(B),        C(═O)R′, C(═NOR″)R′″, —C(═NH)—O—R′″ or benzyl wherein the phenyl        moiety of benzyl is unsubstituted or carries 1, 2, 3, 4, or 5        substituents selected from the group consisting of CN, halogen,        C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,        (C₁-C₄-alkoxy)carbonyl and di(C₁-C₄-alkyl)aminocarbonyl, or    -   two radicals R³ and R⁴ that are bound to the same carbon atom        form together with said carbon atom a saturated or partially        unsaturated 3-, 4-, 5-, 6-, or 7-membered carbocycle or a        saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered        heterocycle, wherein the ring member atoms of the abovementioned        heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms        selected from the group of N, O and S, and wherein the        abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4        substituents selected from halogen, CN, OH, SH, C₁-C₄-alkyl,        C₁-C₄-alkoxy or C₁-C₄-alkylthio; and one or two CH₂ groups of        the abovementioned cycles may be respectively replaced by one or        two C(═O) or C(═S) groups;-   n indicates the number of substituents R^(b) on the phenyl ring and    n is 0, 1, 2, 3 or 4;-   R^(b) is halogen, CN, NO₂, C₁-C₄-alkyl, C₁-C₄-haloalkyl,    C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl,    C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, NR^(A)R^(B), C(═NOR″)R′″ or    —C(═NH)—O—R′″,    -   it being possible for n=2, 3 or 4 that R^(b) are identical or        different;-   Het is a 5- or 6-membered heteroaryl, wherein the ring member atoms    of the heteroaryl include besides carbon atoms 1, 2, 3 or 4    heteroatoms selected from the group of N, O and S and wherein the    heteroaryl is unsubstituted or carries 1, 2, 3 or 4 identical or    different groups R^(c):    -   R^(c) is halogen, CN, NO₂, NH₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl,        C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylamino,        di(C₁-C₆-alkyl)amino, C₁-C₆-alkylthio, C₁-C₆-haloalkylthio,        C₁-C₆-alkylsulfinyl, C₁-C₆-haloalkylsulfinyl,        C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl,        C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-haloalkoxy-C₁-C₄-alkyl,        C₂-C₆-alkenyl, C₂-C₆-alkynyl, C(═O)R′, C(═NOR″)R′″,        C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyl-C₁-C₄-alkyl, phenyl, phenoxy,        phenoxy-C₁-C₄-alkyl or a 5- or 6-membered heteroaryl, wherein        the ring member atoms of the heteroaryl include besides carbon        atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O        and S, and wherein the aforementioned cyclic radicals are        unsubstituted or carry 1, 2, 3 or 4 identical or different        substituents R^(d):    -   R^(d) is halogen, CN, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or        C₁-C₄-haloalkoxy;    -   or two radicals R^(c) that are bound to adjacent ring member        atoms of the Het group form together with said ring member atoms        a fused 5-, 6- or 7-membered saturated, partially unsaturated or        aromatic carbocycle or heterocycle, wherein the ring member        atoms of the fused heterocycle include besides carbon atoms 1,        2, 3 or 4 heteroatoms selected from the group of N, O and S, and        wherein the fused carbocycle or heterocycle is unsubstituted or        carries 1, 2, 3 or 4 identical or different radicals groups        R^(e):    -   R^(e) is halogen, CN, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or        C₁-C₄-haloalkoxy;        and the N-oxides and the agriculturally acceptable salts of the        compounds of formula I.

The present invention furthermore relates to processes for preparingcompounds of formula I. Accordingly a 4-halopyrimidine compound II,wherein Hal is halogen, preferably Cl or F, can be reacted with asuitable phenethyl amine compound III, wherein X is —CR³R⁴—, to obtain acompound I according to the present invention, wherein X is —CR³R⁴—, asshown in Scheme 1.

Generally, this reaction is carried out at temperatures of from 0 to200° C., preferably from 50 to 170° C., in an inert organic solventpreferably in the presence of a base or a catalyst or a combination of abase and a catalyst (catalyst: e.g. NaF, KF, LiF, NaBr, KBr, LiBr, NaI,KI, LiI and ionic liquids, such as imidazolium catalysts).

Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- andp-xylene; halogenated hydro-carbons such as chlorobenzene,dichlorobenzene; ethers such as dioxane, anisole and tetrahydrofuran(THF); nitriles such as acetonitrile and propionitrile; ketones, such asacetone, methyl ethyl ketone, diethyl ketone and tert.-butyl methylketone; alcohols such as ethanol, n-propanol, isopropanol, n-butanol andtert.-butanol; and also dimethyl sulfoxide (DMSO), dimethylformamide(DMF), dimethyl acetamide, N-methyl-2-pyrrolidone (NMP),N-ethyl-2-pyrrolidone (NEP) and acetic acid ethyl ester, preferablyDMSO, DMF, dimethyl acetamide, NMP, or NEP. Particular preference isgiven to NMP. It is also possible to use mixtures of the solventsmentioned.

Suitable bases are, in general, inorganic compounds, such as alkalimetal and alkaline earth metal hydroxides such as lithium hydroxide,sodium hydroxide, potassium hydroxide and calcium hydroxide; alkalimetal and alkaline earth metal oxides such as lithium oxide, sodiumoxide, potassium oxide and calcium oxide; alkali metal and alkalineearth metal phosphates such as lithium phosphate, sodium phosphate,potassium phosphate and calcium phosphate; alkali metal amides such aslithium amide, sodium amide and potassium amide; alkali metal andalkaline earth metal hydrides lithium hydride, sodium hydride, potassiumhydride and calcium hydride; alkali metal and alkaline earth metalcarbonates such as lithium carbonate, potassium carbonate and calciumcarbonate, caesium carbonate; moreover organic bases, for exampletertiary amines such as trimethyl-amine (TMA), triethylamine (TEA),tributylamine (TBA), diisopropylethylamine (DIPEA) andN-methyl-2-pyrrolidone (NMP), pyridine, substituted pyridines such ascollidine, lutidine and 4 dimethylaminopyridine (DMAP), and alsobicyclic amines. Preference is given to sodium hydride, potassiumhydride, lithium carbonate, potassium carbonate, caesium carbonate, TEA,TBA and DIPEA, in particular DIPEA. The bases are generally employed inequimolar amounts, in excess or, if appropriate, as solvent. The amountof base is typically 1.1 to 5.0 molar equivalents relative to 1 mole ofcompounds II.

The starting materials are generally reacted with one another inequimolar amounts. In terms of yields, it may be advantageous to employan excess of compounds III, based on 1.1 to 2.5 equivalents, preferred1.1 to 1.5 equivalents of compounds II.

The compounds II are known from the literature or are commerciallyavailable or they can be prepared for example in analogy to methodsdescribed in: Heterocycles (2009) 78(7), 1627-1665; New J. Chem. (1994)18(6), 701-8; WO 2005/095357; Science of Synthesis (2004) 16, 379-572;WO 2008/156726; WO 2006/072831; Organic Reactions (Hoboken, N.J., UnitedStates) (2000), 56; or Targets in Heterocyclic Systems (2008) 12, 59-84.

The phenethyl amine compounds III are known from the literature or arecommercially available or they can be prepared for example in analogy tomethods described in: WO 2007/046809; WO 2011/025505; or WO 2010/025451.Alternatively, compounds III in which R² is H and X is —CR³R⁴ can beprepared according to the general reaction in scheme 2:

Compound AD-1, in which the phenyl ring bears a hydroxyl group in ortho-or metha-position, is reacted with a heterocycle Het-LG, in which LG isa leaving group such as, e.g. F or Cl, in the presence of a base and/ora catalyst. Or compound AD-2, in which LG is a leaving group inpara-position such as, e.g. F or Cl, is reacted with ahydroxyl-heterocycle HO-Het in the presence of a base and/or a catalystaccording to procedures described in WO 2011032277 A1, WO 2008065393 A1,WO 2007096647 A2, WO 2007006714 A1, AU 2006201959 μl, DE 19518073 A1(with catalyst: Organic Letters (2001), 3(26), 4315-4317; Journal of theAmerican Chemical Society (1999), 121(18), 4369-4378) and providesHet-AD. Subsequent reaction with a nitroalkyl compound followed by areduction leads to amine compounds III as described in TetrahedronLetters (2003), 44(12), 2557-2560, Journal of Mass Spectrometry (2008),43(4), 528-534, WO 2008039882 A1, Bioorganic & Medicinal ChemistryLetters (2007), 17(4), 974-977, Chemistry & Biodiversity (2005), 2(9),1217-1231, Journal of Organic Chemistry (2005), 70(14), 5519-5527,Bioorganic & Medicinal Chemistry (2004), 12(15), 4055-4066 or PesticideScience (1995), 44(4), 341-355.

Otherwise compounds III can be synthesized in analogy to WO 2011053835A1, GB 2059955, WO 2007020227 A1, WO 2008046598 A1, WO 2011053835 A1,European Journal of Medicinal Chemistry (2009), 44(5), 2246-2251,Journal of Medicinal Chemistry (2007), 50(20), 5003-5011.Phenethylamines wherein R¹ and/or R² are not hydrogen are commerciallyavailable or can be prepared as outlined in scheme 3:

By addition of cyanide, a carbonyl compound AD-1 can be transformed intoits cyano hyadrine (Chemistry A European Journal (2011), 17(44),12276-12279; European Journal of Organic Chemistry (2002), (19),3243-3249; Synlett (2003), (3), 353-356; Chirality (2009), 21(9),836-842; Journal of Organic Chemistry (2008), 73(18), 7373-7375).Reduction of the nitrile group provides compounds AD-3 wherein R³ and R⁴are hydrogen. Depending on the reaction conditions, the nitrile in AD-3can be reduced and the hydroxyl group be removed in one step to furnishcompounds III, wherein R³ and R⁴ are both hydrogen (Justus LiebigsAnnalen der Chemie (1949), 564, 49-54, Justus Liebigs Annalen der Chemie(1957), 605, 200-11, Journal of the Chemical Society (1959), 1780-2, WO2007020381 A2). Other conditions allow to preserve the hydroxyl groupwhile selectively reducing the nitrile (Archiv der Pharmazie (Weinheim,Germany, 2011), 344(6), 372-385, Journal of the American ChemicalSociety (1948), 70, 3738-40, Journal of the American Chemical Society(1933), 55, 2593-7, Tetrahedron (2001), 57(40), 8573-8580, Chemical &Pharmaceutical Bulletin (2003), 51(6), 702-709;). This hydroxyl groupcan be transformed in a further step to provide halogen, cyano(Tetrahedron Letters (2007), 48(38), 6779-6784), amino, alkoxy groups bynucleophilic substitution in compounds such as III wherein R³ and R⁴ arehydrogen. It may be advantageous to couple AD-1 or AD-3 with a Het-LGprior to the abovementioned reactions as shown in scheme 2.

Phenethylamine compounds III, in which X is —CR³H— can also be preparedby reductive amination of ketone compounds AD-4 as described in scheme4.

This conversion can be achieved using ammonia and a reducing agent or ametal organic compound or a cyanide source (Journal of the AmericanChemical Society (2011), 133(33), 12914-12917; Acta PharmaceuticaSuecica (1976), 13(1), 65-74; Journal of Medicinal Chemistry (1976),19(6), 763-6; Journal of the American Chemical Society (1952), 74,4611-15).

Phenethylamine compounds of the formula III, in which X is —CR³H—, canalso be prepared by transformation of AD-1 to a nitro alkene AD-6 byfirst reacting it with nitro alkyl compounds AD-5 preferably in thepresence of a base as described in scheme 5 (Journal of OrganicChemistry, 67(14), 4875-4881; 2002; European Journal of MedicinalChemistry, 46(9), 3986-3995; 2011; Journal of the American ChemicalSociety, 107(12), 3601-6; 1985).

Consecutive reduction, e.g. with LiAlH₄ or hydrogen together with asuitable catalyst, leads to phenethylamine compounds III (Organic &Biomolecular Chemistry (2011), 9(23), 8171-8177, Journal of the AmericanChemical Society (2011), 133(31), 12197-12219, European Journal ofMedicinal Chemistry (2010), 45(1), 11-18).

Alternatively, the nitro alkenes AD-6 can be reacted with an alkoxide togive the corresponding alkoxy compounds (European Journal of MedicinalChemistry (2011), 46(9), 3986-3995, Organic Letters (2006), 8(20),4481-4484, Tetrahedron (1999), 55(43), 12493-12514, Journal of OrganicChemistry (1995), 60(13), 4204-12)

Alternatively, the nitro alkenes can be reacted with metal cyanides togive the corresponding cyano compounds (Synlett (2008), (12), 1857-1861,Journal of Organic Chemistry (1985), 50(20), 3878-81). The terminalnitro group can be reduced selectively in the presence of the nitrile toyield compounds III, wherein R² is C₁-C₄-alkoxy or CN, respectively. Itmay be advantageous to couple AD-1 or AD-6 with a Het-LG prior to theabovementioned reactions as shown in scheme 2.

Alternatively, compounds of the formula III, in which X is —CH₂— canalso be prepared by a process as described in scheme 6:

Substituted benzyl nitrile or phenyl acetaldehyde compounds AD-7 can bealkylated (Tetrahedron (1988), 44(15), 4737-46; US 20080171761 A1,Jingxi Huagong Zhongjianti (2010), 40(3), 26-28, Advanced Synthesis &Catalysis (2011), 353(2+3), 501-507) once or twice using alkylationagents which carry a suitable leaving group Y and can then betransformed to the corresponding amine by reduction of the nitrile orimine intermediate respectively (WO 2010081692 A1, Tetrahedron Letters(1985), 26(36), 4299-300; Journal of Organic Chemistry (1981), 46(4),783-8; Tetrahedron (2002), 58(8), 1513-1518). It may be advantageous tocouple AD-7 with a Het-LG prior to the abovementioned reactions as shownin scheme 2.

Furthermore, substituted benzyl nitriles AD-9, which are available frombenzyl halides AD-8, can be used as intermediates for the preparation ofphenethylamines III, wherein R³ and R⁴ are hydrogen, according to scheme7 by way of reduction with an appropriate reducing agent (e.g. LiAlH₄,PhSiH₃ or H₂ and a catalyst: Tetrahedron (2011), 67(42), 8183-8186, WO2011088181 A1, European Journal of Inorganic Chemistry (2011), 2011(22),3381-3386, WO 2008124757 A1).

Further, compounds AD-9 can be used to obtain compounds III wherein atleast one group R³ or R⁴ are not hydrogen. It is well known that benzylnitriles such as AD-9 can undergo a selective addition of alkyl metalssuch as, for example, Grignard reagents R³MgHal, in which Hal stands forchlorine, bromine or iodine, either furnishing compounds III wherein R³is not hydrogen and R⁴ is hydrogen by reduction of an intermediate imineAD-10 with an appropriate reducing agent such as NaBH₄, Bioorganic &Medicinal Chemistry Letters (2011), 21(5), 1434-1437, WO 2010136493 A1,WO 2008034142 A2, Synthesis (1986), (4), 301-3), or, in case an excessof alkyl metal is employed, to directly obtain compounds III, wherein R³and R⁴ are identical and both are, for example, C₁-C₄-alkyl (OrganicProcess Research & Development (2011), 15(4), 871-875, Journal ofMedicinal Chemistry (1999), 42(19), 3965-3970, WO 2009156100 A1).

Compounds III can also be synthesized by way of hydroboration ofsubstituted alkenes AD-12 (scheme 8) followed by Suzuki coupling usingpalladium catalysis (Journal of Organic Chemistry (2007), 72(22),8422-8426; Organic Letters (2007), 9(2), 203-206, Journal of theAmerican Chemical Society (2005), 127(29), 10186-10187).

Compounds I in which X is —CH(C(═O)O—C₁-C₄-alkyl)-, —CH(C(═O)NH₂)—,—CH(C(═O)OH)— or —CHCN— can be prepared as follows or pursuing analogousprocedures as in Scheme 9:

Tert-butyloxycarbonyl protected methyl ester AD-12 can be transformed tothe corresponding biaryl ether AD-13 with suitable heteroaromatic groupsHet-LG in analogy to WO 2005014534 A1, WO 2011100285 A1, TetrahedronLetters (1994), 35(31), 5649-52. The coupling of AD-13 with4-halopyrimidine compound II can be performed in analogy to Journal ofMedicinal Chemistry (2011), 54(15), 5335-5348, Bioorganic & MedicinalChemistry Letters (2011), 21(6), 1741-1743, US 20100068197 A1, WO2005000246 A2, which leads to the formation of compounds I with Q beingC₁-C₄-alkoxy (X is —CH(C(═O)—C₁-C₄-alkoxy)-). Saponificaton of the estergroup with hydroxide bases leads to acid compounds I wherein X is—CH(C(═O)OH)—. Aminolysis of the ester group with ammonia and a catalyst(e.g. potassium cyanide) yields compounds I wherein X is —CH(C(═O)NH₂)—.Dehydratisation of the amide using POCl3 or trifluoro acetic acidanhydride with pyridine or treatment with other reagents capable todehydrate a carboxamide such as, e.g., Burgess's reagent, leads tocompound I, in which X is —CHCN— as described in WO 2006098961 A2.

A 4-halopyrimidine compound II, wherein Hal is halogen, preferably Cl orF, can be reacted with a suitable phenyl acetic acid amide compound III,wherein X is —C(═O)— to obtain a compound IVa

in analogy to scheme 1.

Generally, this reaction is carried out at temperatures of from 0 to200° C., preferably from 50 to 170° C., in an inert organic solventpreferably in the presence of a base or a catalyst or a combination of abase and a catalyst in a solvent.

Suitable catalysts are e.g. halides such as NaF, KF, LiF, NaBr, KBr,LiBr, NaI, KI, LiI; ionic liquids, such as imidazolium catalysts;transition metal catalysts like palladium, rhodium, ruthenium, iron,copper in the form of halides, pseudohalides, alkoxides, carboxylates(preferred acetate), complexes with dibenzylidene acetone and ligandslike phosphine, phosphites, phosphoramidate ligands. Preferred ligandsare bidentate and sterically demanding phosphorous ligands, even morepreferably the catalysts are selected from2,2′-bis(diphenyl-phosphanyl)-1,1′-binaphthyl,2,2′-bis(diphenylphosphino)-1,1′-biphenyl,biphenyl-2-yldicyclohexylphosphine,2-(dicyclohexylphosphino)-2′,6′-dimethoxy-1,1′-biphenyl,1,1-bis(diphenylphosphino)ferrocene,9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene,1,2-bis(diphenylphosphino)ethane (dppe),1,3-propanediylbis[diphenylphosphine],1,4-butanediylbis[diphenylphosphine] and1,1′-(1,2-ethanediyl)bis[1-(2-methoxyphenyl)-1-phenyl-diposphine.

Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- andp-xylene; halogenated hydrocarbons such as chlorobenzene,dichlorobenzene; ethers such as dioxane, anisole and THF; nitriles suchas acetonitrile and propionitrile; ketones such as acetone, methyl ethylketone, diethyl ketone and tert.-butyl methyl ketone; alcohols such asethanol, n-propanol, isopropanol, n-butanol and tert.-butanol; and alsoDMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester.Preferably THF, DMSO, DMF, dimethyl acetamide, NMP or NEP are used; evenmore preferably THF, DMF or NMP are used. It is also possible to usemixtures of the solvents mentioned.

Suitable bases and their amounts are as described for the reaction witha phenethyl amine compound III, wherein X is —CR³R⁴—, as describedabove. The starting materials are generally reacted with one another inequimolar amounts. In terms of yields, it may be advantageous to employan excess of compounds III, based on 1.1 to 2.5 equivalents, preferred1.1 to 1.5 equivalents of compounds II.

The phenyl acetic acid amide compounds IIIa are known from theliterature or are commercially available or they can be prepared forexample in analogy to methods described in Organometallics (2011),30(20), 5442-5451, WO 2010058030 A1 20100527, Journal of OrganicChemistry (1987), 52(21), 4689-93; GB 2016466 A.

Alternatively, amide compounds IVa can be synthesized by reacting4-amino-pyrimidine compounds IIa [available by reaction of achloropyrimidine II with excess of ammonia in analogy to methodsdescribed in WO 2011/147066, WO 2006/135719, US 2005/0245530 A1, J.Chem. Soc. (1951), 3439-44; Helv. Chim. Act. (1951), 34, 835-40] withthe corresponding phenyl acetic acids IIIa in which Z is hydrogen orC₁-C₄-alkyl, which are commercially available, preferably in presence ofAlMe₃ (1 to 3 equivalents) as stoichiometric reagent preferably in aninert organic solvent such as toluene (in analogy to US 2010/0063063 A1;WO 2005/011601; WO 2006/074884) as outlined in Scheme 10.

Compounds IVb can be prepared for example in analogy to methodsdescribed in US 20100022538 A1, J. Med. Chem. (2011), 54(9), 3241-3250,J. Org. Chem. (2011), 76(6), 1546-1553, Org. Lett. (2010), 12(23),5570-5572.

Compounds I, wherein X is —C(═NR^(D))—, can be prepared from compoundsIVa in analogy to Bioorg. Med. Chem. (2008) 16(8), 4600-4616, J. Med.Chem. (2004) 47(3), 663-672, Eur. J. Org. Chem. (2004) 5, 1025-1032, J.Med. Chem. (1987) 30(4), 720-1.

Compounds I, wherein X is —C(═NOR^(D))—, can be prepared from compoundsIVa in analogy to WO 2007/075598 or from compounds IVb according to WO2008/039520 and O'zbekiston Kimyo Jurnali (2004) 4, 3-6.

Compounds I and intermediates, wherein R is hydrogen, can be convertedby conventional processes such as alkylation. Examples of suitablealkylating agents include alkyl halides, such as alkyl chloride, alkylbromide or alkyl iodide, examples being methyl chloride, methyl bromideor methyl iodide, or dialkyl sulfates such as dimethyl sulfate ordiethyl sulfate. The reaction with the alkylating agent is carried outadvantageously in the presence of a solvent. Solvents used for thesereactions are—depending on temperature range—aliphatic, cycloaliphaticor aromatic hydrocarbons such as hexane, cyclohexane, toluene, xylene,chlorinated aliphatic and aromatic hydrocarbons such as DCM,chlorobenzene, open-chain dialkyl ethers such as diethyl ether,di-n-propyl ether, MTBE, cyclic ethers such as THF, 1,4-dioxane, glycolethers such as dimethyl glycol ether, and also DMSO, DMF, dimethylacetamide, NMP, NEP and acetic acid ethyl ester, preferably DMF, DMSO,NMP or NEP, or mixtures of these solvents.

If individual compounds I cannot be obtained by the routes describedabove, they can be prepared by derivatization of other compounds I. TheN-oxides may be prepared from the compounds I according to conventionaloxidation methods, e.g. by treating compounds I with an organic peracidsuch as metachloroperbenzoic acid (cf. WO 03/64572 or J. Med. Chem.(1995), 38(11), 1892-1903,); or with inorganic oxidizing agents such ashydrogen peroxide (cf. J. Heterocyc. Chem. (1981), 18 (7), 1305-1308) oroxone (cf. J. Am. Chem. Soc. (2001), 123 (25), 5962-5973). The oxidationmay lead to pure mono-N-oxides or to a mixture of different N-oxides,which can be separated by conventional methods such as chromatography.

If the synthesis yields mixtures of isomers, a separation is generallynot necessarily required since in some cases the individual isomers canbe interconverted during work-up for use or during application (e.g.under the action of light, acids or bases). Such conversions may alsotake place after use, e.g. in the treatment of plants in the treatedplant, or in the harmful fungus to be controlled.

The reaction mixtures are worked up in a customary manner, for exampleby mixing with water, separating the phases and, if appropriate,chromatic purification of the crude products. In some cases, theintermediates and end products are obtained in the form of colorless orslightly viscous oils which can be freed from volatile components orpurified under reduced pressure and at moderately elevated temperatures.If the intermediates and end products are obtained as solids,purification can also be carried out by recrystallization or digestion.

The compounds of the present invention are useful for combating harmfulfungi. Therefore the present invention furthermore relates to a methodfor combating harmful fungi, which process comprises treating the fungior the materials, plants, the soil or seeds to be protected againstfungal attack, with an effective amount of at least one compound offormula I or of an N-oxide or an agriculturally acceptable salt thereof.

Furthermore, the present invention also relates to seed comprising acompound of formula I, or an N-oxide or an agriculturally acceptablesalt thereof, in an amount of from 0.1 g to 10 kg per 100 kg of seed.

Depending on the substitution pattern, the compounds of formula I andtheir N-oxides may have one or more centers of chirality, in which casethey are present as pure enantiomers or pure diastereomers or asenantiomer or diastereomer mixtures. Both, the pure enantiomers ordiastereomers and their mixtures are subject matter of the presentinvention.

Agriculturally useful salts of the compounds I encompass especially thesalts of those cations or the acid addition salts of those acids whosecations and anions, respectively, have no adverse effect on thefungicidal action of the compounds I. Suitable cations are thus inparticular the ions of the alkali metals, preferably sodium andpotassium, of the alkaline earth metals, preferably calcium, magnesiumand barium, of the transition metals, preferably manganese, copper, zincand iron, and also the ammonium ion which, if desired, may carry one tofour C₁-C₄-alkyl substituents and/or one phenyl or benzyl substituent,preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium,trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions,preferably tri(C₁-C₄-alkyl)sulfonium, and sulfoxonium ions, preferablytri(C₁-C₄-alkyl)sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide,fluoride, hydrogensulfate, sulfate, dihydrogenphosphate,hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate,hexafluorosilicate, hexafluorophosphate, benzoate, and the anions ofC₁-C₄-alkanoic acids, preferably formate, acetate, propionate andbutyrate. They can be formed by reacting a compound I with an acid ofthe corresponding anion, preferably of hydrochloric acid, hydrobromicacid, sulfuric acid, phosphoric acid or nitric acid.

Compounds I can be present in different crystal modifications whosebiological activity may differ. They also form part of the subjectmatter of the present invention. The compounds of formula I can bepresent in atropisomers arising from restricted rotation about a singlebond of asymmetric groups. They also form part of the subject matter ofthe present invention.

In respect of the variables, the embodiments of the intermediatescorrespond to the embodiments of the compounds of formula I. The term“compounds I” refers to compounds of formula I. Likewise, the term“compounds IIa” refers to compounds of formula IIa.

In the definitions of the variables given above, collective terms areused which are generally representative for the substituents inquestion. The term “C_(n)-C_(m)” indicates the number of carbon atomspossible in each case in the substituent or substituent moiety inquestion.

The term “halogen” refers to fluorine, chlorine, bromine and iodine.

The term “C₁-C₄-alkyl” refers to a straight-chained or branchedsaturated hydrocarbon group having 1 to 4 carbon atoms, for examplemethyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,2-methylpropyl, and 1,1-dimethylethyl. Likewise, the term “C₁-C₆-alkyl”refers to a straight-chained or branched saturated hydrocarbon grouphaving 1 to 6 carbon atoms.

The term “C₁-C₄-haloalkyl” refers to a straight-chained or branchedalkyl group having 1 to 4 carbon atoms (as defined above), wherein someor all of the hydrogen atoms in these groups may be replaced by halogenatoms as mentioned above, for example chloromethyl, bromomethyl,dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl,chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl,2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl,2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl,2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl,3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH₂—C₂F₅,CF₂—C₂F₅, CF(CF₃)₂, 1-(fluoromethyl)-2-fluoroethyl,1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl,4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl. Likewise,the term “C₁-C₆-haloalkyl” refers to a straight-chained or branchedalkyl group having 1 to 6 carbon atoms.

The term “C₁-C₄-alkoxy” refers to a straight-chain or branched alkylgroup having 1 to 4 carbon atoms (as defined above) which is bonded viaan oxygen, at any position in the alkyl group, for example methoxy,ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methyl

propoxy, 2-methylpropoxy or 1,1-dimethylethoxy. Likewise, the term“C₁-C₆-alkoxy” refers to a straight-chain or branched alkyl group having1 to 6 carbon atoms.

The term “C₁-C₄-hydroxyalkyl” refers to a straight-chained or branchedalkyl group having 2 to 4 carbon atoms (as defined above), wherein onehydrogen atom in these groups may be replaced by one hydroxy group, forexample hydroxymethyl, 2-hydroxyethyl, 3-hydroxy-propyl,4-hydroxy-butyl.

The term “C₁-C₄-haloalkoxy” refers to a C₁-C₄-alkoxy group as definedabove, wherein some or all of the hydrogen atoms may be replaced byhalogen atoms as mentioned above, for example, OCH₂F, OCHF₂, OCF₃,OCH₂Cl, OCHCl₂, OCCl₃, chlorofluoromethoxy, dichlorofluoromethoxy,chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy,2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy,2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy,2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC₂F₅,2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy,2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy,2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy,3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH₂—C₂F₅, OCF₂—C₂F₅,1-(CH₂F)-2-fluoroethoxy, 1-(CH₂Cl)-2-chloroethoxy, 1-(CH₂Br)-2-bromo

]ethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy ornonafluorobutoxy. Likewise, the term “C₁-C₆-haloalkoxy” refers to aC₁-C₆-alkoxy group as defined above, wherein some or all of the hydrogenatoms may be replaced by halogen atoms as mentioned above.

The term “C₁-C₄-alkoxy-C₁-C₄-alkyl” refers to alkyl having 1 to 4 carbonatoms (as defined above), wherein one hydrogen atom of the alkyl radicalis replaced by a C₁-C₄-alkoxy group (as defined above). Likewise, theterm “C₁-C₆-alkoxy-C₁-C₄-alkyl” refers to alkyl having 1 to 4 carbonatoms (as defined above), wherein one hydrogen atom of the alkyl radicalis replaced by a C₁-C₆-alkoxy group (as defined above).

The term “C₁-C₄-haloalkoxy-C₁-C₄-alkyl” refers to alkyl having 1 to 4carbon atoms (as defined above), wherein one hydrogen atom of the alkylradical is replaced by a C₁-C₄-haloalkoxy group (as defined above).Likewise, the term “C₁-C₆-haloalkoxy-C₁-C₄-alkyl” refers to alkyl having1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of thealkyl radical is replaced by a C₁-C₆-alkoxy group (as defined above).

The term “C₁-C₄-alkylthio” as used herein refers to straight-chain orbranched alkyl groups having 1 to 4 carbon atoms (as defined above)bonded via a sulfur atom, at any position in the alkyl group, forexample methylthio, ethylthio, propylthio, isopropylthio, and nbutylthio. Likewise, the term “C₁-C₆-alkylthio” as used herein refers tostraight-chain or branched alkyl groups having 1 to 6 carbon atoms (asdefined above) bonded via a sulfur atom. Accordingly, the terms“C₁-C₄-haloalkylthio” and “C₁-C₆-haloalkylthio” as used herein refer tostraight-chain or branched haloalkyl groups having 1 to 4 or 1 to 6carbon atoms (as defined above) bonded through a sulfur atom, at anyposition in the haloalkyl group.

The terms “C₁-C₄-alkylsulfinyl” or “C₁-C₆-alkylsulfinyl” refer tostraight-chain or branched alkyl groups having 1 to 4 or 1 to 6 carbonatoms (as defined above) bonded through a —S(═O)-moiety, at any positionin the alkyl group, for example methylsulfinyl and ethylsulfinyl, andthe like. Accordingly, the terms “C₁-C₄-haloalkylsulfinyl” and“C₁-C₆-haloalkylsulfinyl”, respectively, refer to straight-chain orbranched haloalkyl groups having 1 to 4 and 1 to 6 carbon atoms (asdefined above), respectively, bonded through a —S(═O)— moiety, at anyposition in the haloalkyl group.

The terms “C₁-C₄-alkylsulfonyl” and “C₁-C₆-alkylsulfonyl”, respectively,refer to straight-chain or branched alkyl groups having 1 to 4 and 1 to6 carbon atoms (as defined above), respectively, bonded through a—S(═O)₂— moiety, at any position in the alkyl group, for examplemethylsulfonyl. Accordingly, the terms “C₁-C₄-haloalkylsulfonyl” and“C₁-C₆-haloalkylsulfonyl”, respectively, refer to straight-chain orbranched haloalkyl groups having 1 to 4 and 1 to 6 carbon atoms (asdefined above), respectively, bonded through a —S(═O)₂— moiety, at anyposition in the haloalkyl group.

The term “C₁-C₄-alkylamino” refers to an amino radical carrying oneC₁-C₄-alkyl group (as defined above) as substituent, for examplemethylamino, ethylamino, propylamino, 1-methylethylamino, butylamino,1-methylpropylamino, 2-methylpropylamino, 1,1-di-methylethylamino andthe like. Likewise, the term “C₁-C₆-alkylamino” refers to an aminoradical carrying one C₁-C₆-alkyl group (as defined above) assubstituent.

The term “di(C₁-C₄-alkyl)amino” refers to an amino radical carrying twoidentical or different C₁-C₄-alkyl groups (as defined above) assubstituents, for example dimethylamino, diethylamino, di-n-propylamino,diisopropylamino, N-ethyl-N-methylamino, N-(n-propyl)-N-methylamino,N-(isopropyl)-N methylamino, N-(n-butyl)-N-methylamino,N-(n-pentyl)-N-methylamino, N-(2-butyl)-N methylamino,N-(isobutyl)-N-methylamino, and the like. Likewise, the term“di(C₁-C₆-alkyl)amino” refers to an amino radical carrying two identicalor different C₁-C₆-alkyl groups (as defined above) as substituents.

The term “(C₁-C₄-alkoxy)carbonyl” refers to a C₁-C₄-alkoxy radical (asdefined above) which is attached via a carbonyl group.

The term “di(C₁-C₄-alkyl)aminocarbonyl” refers to a di(C₁-C₄)alkylaminoradical as defined above which is attached via a carbonyl group.

The term “phenoxy” and refers to a phenyl radical which is attached viaan oxygen atom. Likewise, the term “phenoxy-C₁-C₄-alkyl” and refers to aphenoxy radical which is attached via a C₁-C₄-alkyl group (as definedabove).

The term “C₂-C₄-alkenyl” refers to a straight-chain or branchedunsaturated hydrocarbon radical having 2 to 4 carbon atoms and a doublebond in any position, such as ethenyl, 1-propenyl, 2-propenyl (allyl),1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl. Likewise,the term “C₂-C₆-alkenyl” refers to a straight-chain or branchedunsaturated hydrocarbon radical having 2 to 6 carbon atoms and a doublebond in any position.

The term “C₂-C₄-alkynyl” refers to a straight-chain or branchedunsaturated hydrocarbon radical having 2 to 4 carbon atoms andcontaining at least one triple bond, such as ethynyl, 1-propynyl,2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl.Likewise, the term “C₂-C₆-alkynyl” refers to a straight-chain orbranched unsaturated hydrocarbon radical having 2 to 6 carbon atoms andat least one triple bond.

The term “C₃-C₈-cycloalkyl” refers to monocyclic saturated hydrocarbonradicals having 3 to 8 carbon ring members, such as cyclopropyl (C₃H₅),cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The term “C₃-C₈-cycloalkyl-C₁-C₄-alkyl” refers to a cycloalkyl radicalhaving 3 to 8 carbon atoms (as defined above), which is bonded via aC₁-C₄-alkyl group (as defined above).

The term “C₃-C₈-cycloalkyloxy” refers to a cycloalkyl radical having 3to 8 carbon atoms (as defined above), which is bonded via an oxygen.

The term “saturated or partially unsaturated 3-, 4-5-, 6- or 7-memberedcarbocycle” is to be understood as meaning both saturated or partiallyunsaturated carbocycles having 3, 4, 5, 6 or 7 ring members. Examplesinclude cyclopropyl, cyclopentyl, cyclopentenyl, cyclopentadienyl,cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptenyl,cycloheptadienyl, and the like.

The term “saturated or partially unsaturated 3-, 4-, 5-, 6-, or7-membered heterocycle, wherein the ring member atoms of the heterocycleinclude besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from thegroup of N, O and S”, is to be understood as meaning both saturated andpartially unsaturated heterocycles, for example:

-   -   a 3- or 4-membered saturated heterocycle which contains 1 or 2        heteroatoms from the group consisting of N, O and S as ring        members such as oxirane, aziridine, thiirane, oxetane,        azetidine, thiethane, [1,2]dioxetane, [1,2]dithietane,        [1,2]diazetidine; and    -   a 5- or 6-membered saturated or partially unsaturated        heterocycle which contains 1, 2 or 3 heteroatoms from the group        consisting of N, O and S as ring members such as        2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl,        3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl,        3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl,        3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl,        3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl,        2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl,        4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl,        4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl,        1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl,        1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl,        1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl,        1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl,        2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl,        2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl,        2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl,        2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl,        2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl,        2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl,        2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl,        2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl,        2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl,        2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl,        2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl,        2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl,        2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl,        3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl,        3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl,        4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl,        4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl,        2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl,        2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,        3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl,        3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,        3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl,        3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl,        2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl,        3-hexahydropyridazinyl, 4-hexahydropyridazinyl,        2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl,        5-hexahydropyrimidinyl, 2-piperazinyl,        1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl and        also the corresponding—ylidene radicals; and    -   a 7-membered saturated or partially unsaturated heterocycle such        as tetra- and hexahydroazepinyl, such as        2,3,4,5-tetrahydro[1H]azepin-1-,-2-,-3-,-4-,-5-,-6- or -7-yl,        3,4,5,6-tetrahydro[2H]azepin-2-,-3-,-4-,-5-,-6- or -7-yl,        2,3,4,7-tetrahydro[1H]azepin-1-,-2-,-3-,-4-,-5-,-6- or -7-yl,        2,3,6,7-tetrahydro[1H]azepin-1-,-2-,-3-,-4-,-5-,-6- or -7-yl,        hexahydroazepin-1-,-2-,-3- or -4-yl, tetra- and        hexahydrooxepinyl such as        2,3,4,5-tetrahydro[1H]oxepin-2-,-3-,-4-,-5-,-6- or -7-yl,        2,3,4,7-tetrahydro[1H]oxepin-2-,-3-,-4-,-5-,-6- or -7-yl,        2,3,6,7-tetrahydro[1H]oxepin-2-, -3-,-4-,-5-,-6- or -7-yl,        hexahydroazepin-1-,-2-,-3- or -4-yl, tetra- and        hexahydro-1,3-diazepinyl, tetra- and hexahydro-1,4-diazepinyl,        tetra- and hexahydro-1,3-oxazepinyl, tetra- and        hexahydro-1,4-oxazepinyl, tetra- and hexahydro-1,3-dioxepinyl,        tetra- and hexahydro-1,4-dioxepinyl and the        corresponding—ylidene radicals; and

The term “5- or 6-membered heteroaryl, wherein the ring member atoms ofthe heteroaryl include besides carbon atoms 1, 2, 3 or 4 heteroatomsselected from the group of N, O and S”, refers to, for example,

-   -   a 5-membered heteroaryl such as pyrrol-1-yl, pyrrol-2-yl,        pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl,        pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl,        imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl,        oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl,        isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl,        thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl,        1,2,4-triazolyl-1-yl, 1,2,4-triazol-3-yl 1,2,4-triazol-5-yl,        1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl and        1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl; or    -   a 6-membered heteroaryl, such as pyridin-2-yl, pyridin-3-yl,        pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl,        pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and        1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl.

The term “two radicals R^(c) that are bound to adjacent ring memberatoms form together with said ring member atoms a fused cycle” refers toa condensed bicyclic ring system, wherein 5- or 6-membered heteroarylcarries a fused-on 5-, 6- or 7-membered carbocyclic or heterocyclic ringit being possible that these rings are saturated or partially saturatedor aromatic.

The term “one or two CH₂ groups of the abovementioned cycles may berespectively replaced by one or two C(═O) or C(═S) groups” refers to anexchange of carbon atoms from a saturated or partially unsaturated 3-,4-, 5-, 6- or 7-membered carbocycle or a saturated or partiallyunsaturated 3-, 4-, 5-, 6- or 7-membered heterocycle, resulting incycles such as cyclopropanone, cyclopentanone, cyclopropanethione,cyclopentanethione, 5-oxazolone, cyclohexane-1,4-dione,cyclohexane-1,4-dithione, cyclohex-2-ene-1,4-dione orcyclohex-2-ene-1,4-dithione.

As regards the fungicidal activity of the compounds I, I.A, I.B or I.Cpreference is given to those compounds, wherein the substituents andvariables (e.g. R^(a2), R^(a5), R^(a6), R, X, R¹, R², R³, R⁴, R^(b),R^(c), R′, R′″, R^(A), R^(B), R^(D), Het, n) have independently of eachother or more preferably in combination the following meanings:

A further embodiment relates to compounds I wherein R^(a2) and R^(a5)independently of each other are preferably selected from the groupconsisting of hydrogen, halogen, CN, C₁-C₄-alkoxy,C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₂-C₄-alkenyl, C₂-C₄-alkynyl,C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyloxy, (C₁-C₄-alkoxy)carbonyl. Furtherpreferred embodiments relate to compounds I wherein R^(a2) and R^(a5)independently of each other are hydrogen, halogen, CN, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkoxy and(C₁-C₄-alkoxy)carbonyl. Further preferred embodiments relate tocompounds I wherein R^(a2) and R^(a5) independently of each other arehalogen, CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalk-oxy, C₁-C₄-alkoxy-C₁-C₄-alkoxy or (C₁-C₄-alkoxy)carbonyl,and it being possible that one of both, R^(a2) or R^(a5) can in additionbe hydrogen. Further preferred embodiments relate to compounds I whereinR^(a2) and R^(a5) independently of each other are hydrogen, Cl, F, CH₃,CH₂CH₃, OCH₃, OCF₃, CH₂OCH₃, CN, OCH₂OCH, CF₃, CHFCH₃, COOCH₃ orCOOCH₂CH₃.

Further preferred embodiments relate to compounds I wherein R^(a5) isCl.

Further preferred embodiments relate to compounds I wherein R^(a5) is F.

Further preferred embodiments relate to compounds I wherein R^(a5) isCH₃.

Further preferred embodiments relate to compounds I wherein R^(a5) isOCH₃.

In the compounds I according to the invention, R^(A), R^(B) in radicalsR^(a2) and R^(a5) independently of one another preferably are hydrogen,C₁-C₄-alkyl.

In the compounds I according to the invention, R′ in radicals R^(a2) andR^(a5) preferably is hydrogen, NH₂, C₁-C₄-alkyl, C₁-C₄-alkoxy. In thecompounds I according to the invention, R″ in radicals R^(a2) and R^(a5)preferably is hydrogen, C₁-C₄-alkyl. In the compounds I according to theinvention, R″ in radicals R^(a2) and R^(a5) preferably is hydrogen.

Further preferred embodiments relate to compounds I wherein R^(a2) andR^(a5) in each case are one of the following combinations in line 1 toline 196 in table A:

TABLE A line R^(a2) R^(a5) 1 H H 2 CH₃ H 3 CH₂CH₃ H 4 OCH₃ H 5 CH₂OCH₃ H6 OCH₂OCH₃ H 7 CF₃ H 8 CHFCH₃ H 9 CN H 10 F H 11 Cl H 12 COOCH₃ H 13COOCH₂CH₃ H 14 OCF₃ H 15 H CH₃ 16 CH₃ CH₃ 17 CH₂CH₃ CH₃ 18 OCH₃ CH₃ 19CH₂OCH₃ CH₃ 20 OCH₂OCH₃ CH₃ 21 CF₃ CH₃ 22 CHFCH₃ CH₃ 23 CN CH₃ 24 F CH₃25 Cl CH₃ 26 COOCH₃ CH₃ 27 COOCH₂CH₃ CH₃ 28 OCF₃ CH₃ 29 H CH₂CH₃ 30 CH₃CH₂CH₃ 31 CH₂CH₃ CH₂CH₃ 32 OCH₃ CH₂CH₃ 33 CH₂OCH₃ CH₂CH₃ 34 OCH₂OCH₃CH₂CH₃ 35 CF₃ CH₂CH₃ 36 CHFCH₃ CH₂CH₃ 37 CN CH₂CH₃ 38 F CH₂CH₃ 39 ClCH₂CH₃ 40 COOCH₃ CH₂CH₃ 41 COOCH₂CH₃ CH₂CH₃ 42 OCF₃ CH₂CH₃ 43 H OCH₃ 44CH₃ OCH₃ 45 CH₂CH₃ OCH₃ 46 OCH₃ OCH₃ 47 CH₂OCH₃ OCH₃ 48 OCH₂OCH₃ OCH₃ 49CF₃ OCH₃ 50 CHFCH₃ OCH₃ 51 CN OCH₃ 52 F OCH₃ 53 Cl OCH₃ 54 COOCH₃ OCH₃55 COOCH₂CH₃ OCH₃ 56 OCF₃ OCH₃ 57 H CH₂OCH₃ 58 CH₃ CH₂OCH₃ 59 CH₂CH₃CH₂OCH₃ 60 OCH₃ CH₂OCH₃ 61 CH₂OCH₃ CH₂OCH₃ 62 OCH₂OCH₃ CH₂OCH₃ 63 CF₃CH₂OCH₃ 64 CHFCH₃ CH₂OCH₃ 65 CN CH₂OCH₃ 66 F CH₂OCH₃ 67 Cl CH₂OCH₃ 68COOCH₃ CH₂OCH₃ 69 COOCH₂CH₃ CH₂OCH₃ 70 OCF₃ CH₂OCH₃ 71 H OCH₂OCH₃ 72 CH₃OCH₂OCH₃ 73 CH₂CH₃ OCH₂OCH₃ 74 OCH₃ OCH₂OCH₃ 75 CH₂OCH₃ OCH₂OCH₃ 76OCH₂OCH₃ OCH₂OCH₃ 77 CF₃ OCH₂OCH₃ 78 CHFCH₃ OCH₂OCH₃ 79 CN OCH₂OCH₃ 80 FOCH₂OCH₃ 81 Cl OCH₂OCH₃ 82 COOCH₃ OCH₂OCH₃ 83 COOCH₂CH₃ OCH₂OCH₃ 84 OCF₃OCH₂OCH₃ 85 H CF₃ 86 CH₃ CF₃ 87 CH₂CH₃ CF₃ 88 OCH₃ CF₃ 89 CH₂OCH₃ CF₃ 90OCH₂OCH₃ CF₃ 91 CF₃ CF₃ 92 CHFCH₃ CF₃ 93 CN CF₃ 94 F CF₃ 95 Cl CF₃ 96COOCH₃ CF₃ 97 COOCH₂CH₃ CF₃ 98 OCF₃ CF₃ 99 H CHFCH₃ 100 CH₃ CHFCH₃ 101CH₂CH₃ CHFCH₃ 102 OCH₃ CHFCH₃ 103 CH₂OCH₃ CHFCH₃ 104 OCH₂OCH₃ CHFCH₃ 105CF₃ CHFCH₃ 106 CHFCH₃ CHFCH₃ 107 CN CHFCH₃ 108 F CHFCH₃ 109 Cl CHFCH₃110 COOCH₃ CHFCH₃ 111 COOCH₂CH₃ CHFCH₃ 112 OCF₃ CHFCH₃ 113 H CN 114 CH₃CN 115 CH₂CH₃ CN 116 OCH₃ CN 117 CH₂OCH₃ CN 118 OCH₂OCH₃ CN 119 CF₃ CN120 CHFCH₃ CN 121 CN CN 122 F CN 123 Cl CN 124 COOCH₃ CN 125 COOCH₂CH₃CN 126 OCF₃ CN 127 H F 128 CH₃ F 129 CH₂CH₃ F 130 OCH₃ F 131 CH₂OCH₃ F132 OCH₂OCH₃ F 133 CF₃ F 134 CHFCH₃ F 135 CN F 136 F F 137 Cl F 138COOCH₃ F 139 COOCH₂CH₃ F 140 OCF₃ F 141 H Cl 142 CH₃ Cl 143 CH₂CH₃ Cl144 OCH₃ Cl 145 CH₂OCH₃ Cl 146 OCH₂OCH₃ Cl 147 CF₃ Cl 148 CHFCH₃ Cl 149CN Cl 150 F Cl 151 Cl Cl 152 COOCH₃ Cl 153 COOCH₂CH₃ Cl 154 OCF₃ Cl 155H COOCH₃ 156 CH₃ COOCH₃ 157 CH₂CH₃ COOCH₃ 158 OCH₃ COOCH₃ 159 CH₂OCH₃COOCH₃ 160 OCH₂OCH₃ COOCH₃ 161 CF₃ COOCH₃ 162 CHFCH₃ COOCH₃ 163 CNCOOCH₃ 164 F COOCH₃ 165 Cl COOCH₃ 166 COOCH₃ COOCH₃ 167 COOCH₂CH₃ COOCH₃168 OCF₃ COOCH₃ 169 H COOCH₂CH₃ 170 CH₃ COOCH₂CH₃ 171 CH₂CH₃ COOCH₂CH₃172 OCH₃ COOCH₂CH₃ 173 CH₂OCH₃ COOCH₂CH₃ 174 OCH₂OCH₃ COOCH₂CH₃ 175 CF₃COOCH₂CH₃ 176 CHFCH₃ COOCH₂CH₃ 177 CN COOCH₂CH₃ 178 F COOCH₂CH₃ 179 ClCOOCH₂CH₃ 180 COOCH₃ COOCH₂CH₃ 181 COOCH₂CH₃ COOCH₂CH₃ 182 OCF₃COOCH₂CH₃ 183 H OCF₃ 184 CH₃ OCF₃ 185 CH₂CH₃ OCF₃ 186 OCH₃ OCF₃ 187CH₂OCH₃ OCF₃ 188 OCH₂OCH₃ OCF₃ 189 CF₃ OCF₃ 190 CHFCH₃ OCF₃ 191 CN OCF₃192 F OCF₃ 193 Cl OCF₃ 194 COOCH₃ OCF₃ 195 COOCH₂CH₃ OCF₃ 196 OCF₃ OCF₃

In the compounds I according to the invention, R^(a6) preferably ischlorine.

In the compounds I according to the invention, R^(a6) preferably isfluorine.

In the compounds I according to the invention, R^(a6) preferably isbromine.

In the compounds I according to the invention, R is preferably selectedfrom the group consisting of hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-alkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, CN, CH₂CN orCH₂—O—C(═O)R′, wherein R′ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy; morepreferably R is selected from the group consisting of hydrogen,C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl and C₂-C₄-alkynyl;most preferably R is hydrogen or C₁-C₄-alkyl.

Another particularly preferred embodiment relates to compounds I whereinR is hydrogen; yet another preferred embodiment relates to compounds Iwherein R is CH₃. Further preferred embodiments relate to compounds Iwherein R is in each case one of the following groups I-1 to I-2 intable I:

TABLE I No. R I-1 H I-2 CH₃

In the compounds I according to the invention, X is preferably —CH₂—,—CH(CH₃)—, —CH(CH₂CH₃)—, —C(CH₃)₂—, —CHCN—, —CH(C(═O)—C₁-C₄-alkoxy)-,—CH(C(═O)NH₂)—, —C(═O)N(C₁-C₄-alkyl)₂- and —CH(C(═O)OH)—; morepreferably X is —CH₂— or —CH(CH₂OH)—, in particular X is —CH₂—. Furtherpreferred embodiments relate to compounds I wherein X is in each caseone of the following groups II-1 to II-7 in table II:

TABLE II No. X II-1 —CH₂— II-2 —C(═O)— II-3 —CH(CH₃)— II-4 —C(CH₃)₂—II-5 —CH(C₂H₅)— II-6 —CHCN— II-7 —CH(CH₂OH)—

In the compounds I according to the invention, R¹ and R² independentlyof each other are preferably selected from the group consisting ofhydrogen, halogen, CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy and C₃-C₈-cycloalkyl; more preferably R¹ and R²independently of each other are hydrogen, CN, CH₃, CH₂CH₃, F, Cl orOCH₃; another more preferred embodiment relates to compounds I whereinR¹ and R² independently of each other are hydrogen or CH₃; morepreferably R¹ and R² are hydrogen.

Further preferred embodiments relate to compounds I wherein R¹ and R² ineach case are one of the following combinations III-1 to III-7 in tableIII:

TABLE III No. R¹ R² III-1 H H III-2 CH₃ H III-3 CN H III-4 F H III-5 ClH III-6 OCH₃ H III-7 CH₃ CH₃

In the compounds I according to the invention, R^(b) is preferablyselected from the group consisting of halogen, CN, NO₂, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy and C₁-C₄-alkoxy-C₁-C₄-alkyl; more preferably R^(b) isselected from the group consisting of halogen, CN, C₁-C₄-haloalkyl andC₁-C₄-alkoxy; most preferably R^(b) is halogen, CN, CH₃, CF₃, OCH₃.

In the compounds I according to the invention, n is preferably 0.

A further embodiment relates to compounds I wherein n is preferably 1.

A further embodiment relates to compounds I wherein n is preferably 2.

A further embodiment relates to compounds I wherein n is preferably 3.

A further embodiment relates to compounds I wherein n is preferably 4.

In the compounds I according to the invention, Het is preferablyselected from the group consisting of pyrimidin-2-yl, pyrimidin-3-yl,pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiazol-2-yl,thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl,isothiazol-5-yl, pyrazin-2-yl, pyridazin-3-yl, 1,3,5-triazin-2-yl, and1,2,4-triazin-3-yl; more preferably Het is selected from pyrimidin-2-yl,pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl,pyridin-4-yl, thiazol-2-yl, pyrazin-2-yl, pyridazin-3-yl,1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl; preferably Het ispyrimidin-2-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiazol-2-yl;more preferably Het is unsubstituted; a further preferred embodimentrelates to compounds I wherein Het is substituted by 1 radical R^(c);another preferred embodiment relates to compounds I wherein Het issubstituted by 2 radicals R^(c); yet another preferred embodimentrelates to compounds I wherein Het is substituted by 3 radicals R^(c);another preferred embodiment relates to compounds I wherein Het issubstituted by 4 radicals R.

Preferred embodiments of the invention relate to compounds I, in whichthe group Het is one of the following radicals H-1 to H-38 in table H:

TABLE H No. Het H-1 

H-2 

H-3 

H-4 

H-5 

H-6 

H-7 

H-8 

H-9 

H-10

H-11

H-12

H-13

H-14

H-15

H-16

H-17

H-18

H-19

H-20

H-21

H-22

H-23

H-24

H-25

H-26

H-27

H-28

H-29

H-30

H-31

H-32

H-33

H-34

H-35

H-36

H-37

H-38

in which # indicates the point of attachment.

In the compounds I according to the invention, R^(c) is preferablyselected from the group consisting of halogen, CN, C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyl,C₂-C₆-alkynyl, C(═O)R′, C(═NOR″)R′″, C₃-C₈-cycloalkyl, phenyl andphenoxy. A further embodiment relates to compounds I wherein R^(c) is F,Cl, CN, CH₃, OCH₃, CF₃, OCF₃ or COOCH₃; most preferably R^(c) is Cl, CN,CF₃.

With respect to their use, particular preference is given to thecompounds I.A:

With respect to their use, particular preference is also given to thecompounds I.B:

With respect to their use, particular preference is also given to thecompounds I.C:

According to a further embodiment, the present invention relates tocompounds of the formula I.A wherein:

-   R^(a2), R^(a5) independently of each other are hydrogen, halogen,    CN, NH₂, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,    C₁-C₄-haloalkoxy or (C₁-C₄-alkoxy)carbonyl;-   R^(a6) is halogen;-   R is hydrogen or C₁-C₄-alkyl;-   X is a divalent group —CR³R⁴—; wherein    -   R³, R⁴ independently of each other are hydrogen, C₁-C₄-alkyl,        C₁-C₄-hydroxyalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl or        (C₁-C₄-alkoxy)carbonyl;-   R¹, R² independently of each other are hydrogen or C₁-C₄-alkyl;-   n indicates the number of substituents R^(b) on the phenyl ring and    n is 0 or 1;-   R^(b) is halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy;-   Het is a pyridinyl or pyrimidinyl wherein the pyridinyl or    pyrimidinyl is unsubstituted or carries 1 or 2 groups R^(c):    -   R^(c) is halogen, CN, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy        or C₁-C₆-haloalkoxy; and        the N-oxides and the agriculturally acceptable salts of the        compounds of formula I.A.

The compounds I and the compositions according to the invention,respectively, are suitable as fungicides. They are distinguished by anoutstanding effectiveness against a broad spectrum of phytopathogenicfungi, including soil-borne fungi, which derive especially from theclasses of the Plasmodiophoromycetes, Peronosporomycetes (syn.Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetesand Deuteromycetes (syn. Fungi imperfecti). Some are systemicallyeffective and they can be used in crop protection as foliar fungicides,fungicides for seed dressing and soil fungicides. Moreover, they aresuitable for controlling harmful fungi, which inter alia occur in woodor roots of plants.

The compounds I and the compositions according to the invention areparticularly important in the control of a multitude of phytopathogenicfungi on various cultivated plants, such as cereals, e.g. wheat, rye,barley, triticale, oats or rice; beet, e.g. sugar beet or fodder beet;fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries,blackberries or gooseberries; leguminous plants, such as lentils, peas,alfalfa or soybeans; oil plants, such as rape, mustard, olives,sunflowers, coconut, cocoa beans, castor oil plants, oil palms, groundnuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiberplants, such as cotton, flax, hemp or jute; citrus fruit, such asoranges, lemons, grapefruits or mandarins; vegetables, such as spinach,lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes,cucurbits or paprika; lauraceous plants, such as avocados, cinnamon orcamphor; energy and raw material plants, such as corn, soybean, rape,sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines(table grapes and grape juice grape vines); hop; turf; sweet leaf (alsocalled Stevia); natural rubber plants or ornamental and forestry plants,such as flowers, shrubs, broad-leaved trees or evergreens, e.g.conifers; and on the plant propagation material, such as seeds, and thecrop material of these plants. Preferably, compounds I and compositionsthereof, respectively are used for controlling a multitude of fungi onfield crops, such as potatoes sugar beets, tobacco, wheat, rye, barley,oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee orsugar cane; fruits; vines; ornamentals; or vegetables, such ascucumbers, tomatoes, beans or squashes.

The term “plant propagation material” is to be understood to denote allthe generative parts of the plant such as seeds and vegetative plantmaterial such as cuttings and tubers (e.g. potatoes), which can be usedfor the multiplication of the plant. This includes seeds, roots, fruits,tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants,including seedlings and young plants, which are to be transplanted aftergermination or after emergence from soil.

These young plants may also be protected before transplantation by atotal or partial treatment by immersion or pouring.

Preferably, treatment of plant propagation materials with compounds Iand compositions thereof, respectively, is used for controlling amultitude of fungi on cereals, such as wheat, rye, barley and oats;rice, corn, cotton and soybeans.

The term “cultivated plants” is to be understood as including plantswhich have been modified by breeding, mutagenesis or genetic engineeringincluding but not limiting to agricultural biotech products on themarket or in development (cf.http://www.bio.org/speeches/pubs/er/agri_products.asp). Geneticallymodified plants are plants, which genetic material has been so modifiedby the use of recombinant DNA techniques that under naturalcircumstances cannot readily be obtained by cross breeding, mutations ornatural recombination. Typically, one or more genes have been integratedinto the genetic material of a genetically modified plant in order toimprove certain properties of the plant. Such genetic modifications alsoinclude but are not limited to targeted post-translational modificationof protein(s), oligo- or polypeptides e.g. by glycosylation or polymeradditions such as prenylated, acetylated or farnesylated moieties or PEGmoieties.

The compounds I and compositions thereof, respectively, are particularlysuitable for controlling the following plant diseases:

Albugo spp. (white rust) on ornamentals, vegetables (e.g. A. candida)and sunflowers (e.g. A. tragopogonis); Alternaria spp. (Alternaria leafspot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A.tenuis), fruits, rice, soybeans, potatoes (e.g. A. solani or A.alternata), tomatoes (e.g. A. solani or A. alternata) and wheat;Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. oncereals and vegetables, e.g. A. tritici (anthracnose) on wheat and A.hordei on barley; Bipolaris and Drechslera spp. (teleomorph:Cochliobolus spp.), e.g. Southern leaf blight (D. maydis) or Northernleaf blight (B. zeicola) on corn, e.g. spot blotch (B. sorokiniana) oncereals and e.g. B. oryzae on rice and turfs; Blumeria (formerlyErysiphe) graminis (powdery mildew) on cereals (e.g. on wheat orbarley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: greymold) on fruits and berries (e.g. strawberries), vegetables (e.g.lettuce, carrots, celery and cabbages), rape, flowers, vines, forestryplants and wheat; Bremia lactucae (downy mildew) on lettuce;Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved treesand evergreens, e.g. C. ulmi (Dutch elm disease) on elms; Cercosporaspp. (Cercospora leaf spots) on corn (e.g. Gray leaf spot: C.zeae-maydis), rice, sugar beets (e.g. C. beticola), sugar cane,vegetables, coffee, soybeans (e.g. C. sojina or C. kikuchii) and rice;Cladosporium spp. on tomatoes (e.g. C. fulvum: leaf mold) and cereals,e.g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) oncereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp.(leaf spots) on corn (C. carbonum), cereals (e.g. C. sativus, anamorph:B. sorokiniana) and rice (e.g. C. miyabeanus, anamorph: H. oryzae);Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton(e.g. C. gossypii), corn (e.g. C. graminicola: Anthracnose stalk rot),soft fruits, potatoes (e.g. C. coccodes: black dot), beans (e.g. C.lindemuthianum) and soybeans (e.g. C. truncatum or C. gloeosporioides);Corticium spp., e.g. C. sasakii (sheath blight) on rice; Corynesporacassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp.,e.g. C. oleaginum on olive trees; Cylindrocarpon spp. (e.g. fruit treecanker or young vine decline, teleomorph: Nectria or Neonectria spp.) onfruit trees, vines (e.g. C. liriodendri, teleomorph: Neonectrialiriodendri: Black Foot Disease) and ornamentals; Dematophora(teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans;Diaporthe spp., e.g. D. phaseolorum (damping off) on soybeans;Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. oncorn, cereals, such as barley (e.g. D. teres, net blotch) and wheat(e.g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback,apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F.mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremoniumchlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeriaobtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta:anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leafsmut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp.(powdery mildew) on sugar beets (E. betae), vegetables (e.g. E. pisi),such as cucurbits (e.g. E. cichoracearum), cabbages, rape (e.g. E.cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph:Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines andornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e.g.E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stemrot) on various plants, such as F. graminearum or F. culmorum (root rot,scab or head blight) on cereals (e.g. wheat or barley), F. oxysporum ontomatoes, F. solani on soybeans and F. verticillioides on corn;Gaeumannomyces graminis (take-all) on cereals (e.g. wheat or barley) andcorn; Gibberella spp. on cereals (e.g. G. zeae) and rice (e.g. G.fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruitsand other plants and G. gossypii on cotton; Grainstaining complex onrice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. onrosaceous plants and junipers, e.g. G. sabinae (rust) on pears;Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) oncorn, cereals and rice; Hemileia spp., e.g. H. vastatrix (coffee leafrust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) onvines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) onsoybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snowmold) on cereals (e.g. wheat or barley); Microsphaera diffusa (powderymildew) on soybeans; Monilinia spp., e.g. M. laxa, M. fructicola and M.fructigena (bloom and twig blight, brown rot) on stone fruits and otherrosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruitsand ground nuts, such as e.g. M. graminicola (anamorph: Septoriatritici, Septoria blotch) on wheat or M. fijiensis (black Sigatokadisease) on bananas; Peronospora spp. (downy mildew) on cabbage (e.g. P.brassicae), rape (e.g. P. parasitica), onions (e.g. P. destructor),tobacco (P. tabacina) and soybeans (e.g. P. manshurica); Phakopsorapachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp.e.g. on vines (e.g. P. tracheiphila and P. tetraspora) and soybeans(e.g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rapeand cabbage and P. betae (root rot, leaf spot and damping-off) on sugarbeets; Phomopsis spp. on sunflowers, vines (e.g. P. viticola: can andleaf spot) and soybeans (e.g. stem rot: P. phaseoli, teleomorph:Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn;Phytophthora spp. (wilt, root, leaf, fruit and stem root) on variousplants, such as paprika and cucurbits (e.g. P. capsici), soybeans (e.g.P. megasperma, syn. P. sojae), potatoes and tomatoes (e.g. P. infestans:late blight) and broad-leaved trees (e.g. P. ramorum: sudden oak death);Plasmodiophora brassicae (club root) on cabbage, rape, radish and otherplants; Plasmopara spp., e.g. P. viticola (grapevine downy mildew) onvines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew)on rosaceous plants, hop, pome and soft fruits, e.g. P. leucotricha onapples; Polymyxa spp., e.g. on cereals, such as barley and wheat (P.graminis) and sugar beets (P. betae) and thereby transmitted viraldiseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph:Tapesia yallundae) on cereals, e.g. wheat or barley; Pseudoperonospora(downy mildew) on various plants, e.g. P. cubensis on cucurbits or P.humili on hop; Pseudopezicula tracheiphila (red fire disease or‘rotbrenner’, anamorph: Phialophora) on vines; Puccinia spp. (rusts) onvarious plants, e.g. P. triticina (brown or leaf rust), P. striiformis(stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem orblack rust) or P. recondita (brown or leaf rust) on cereals, such ase.g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P.asparagi on asparagus; Pyrenophora (anamorph: Drechslera)tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley;Pyricularia spp., e.g. P. oryzae (teleomorph: Magnaporthe grisea, riceblast) on rice and P. grisea on turf and cereals; Pythium spp.(damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers,soybeans, sugar beets, vegetables and various other plants (e.g. P.ultimum or P. aphani-dermatum); Ramularia spp., e.g. R. collo-cygni(Ramularia leaf spots, Physiological leaf spots) on barley and R.beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes,turf, corn, rape, potatoes, sugar beets, vegetables and various otherplants, e.g. R. solani (root and stem rot) on soybeans, R. solani(sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) onwheat or barley; Rhizopus stolonifer (black mold, soft rot) onstrawberries, carrots, cabbage, vines and tomatoes; Rhynchosporiumsecalis (scald) on barley, rye and triticale; Sarocladium oryzae and S.attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or whitemold) on vegetables and field crops, such as rape, sunflowers (e.g. S.sclerotiorum) and soybeans (e.g. S. rolfsii or S. sclerotiorum);Septoria spp. on various plants, e.g. S. glycines (brown spot) onsoybeans, S. tritici (Septoria blotch) on wheat and S. (syn.Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn.Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines;Setospaeria spp. (leaf blight) on corn (e.g. S. turcicum, syn.Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn,(e.g. S. reiliana: head smut), sorghum and sugar cane; Sphaerothecafuliginea (powdery mildew) on cucurbits; Spongospora subterranea(powdery scab) on potatoes and thereby transmitted viral diseases;Stagonospora spp. on cereals, e.g. S. nodorum (Stagonospora blotch,teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat;Synchytrium endobioticum on potatoes (potato wart disease); Taphrinaspp., e.g. T. deformans (leaf curl disease) on peaches and T. pruni(plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco,pome fruits, vegetables, soybeans and cotton, e.g. T. basicola (syn.Chalara elegans); Tilletia spp. (common bunt or stinking smut) oncereals, such as e.g. T. tritici (syn. T. caries, wheat bunt) and T.controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) onbarley or wheat; Urocystis spp., e.g. U. occulta (stem smut) on rye;Uromyces spp. (rust) on vegetables, such as beans (e.g. U.appendiculatus, syn. U. phaseoli) and sugar beets (e.g. U. betae);Ustilago spp. (loose smut) on cereals (e.g. U. nuda and U. avaenae),corn (e.g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) onapples (e.g. V. inaequalis) and pears; and Verticillium spp. (wilt) onvarious plants, such as fruits and ornamentals, vines, soft fruits,vegetables and field crops, e.g. V. dahliae on strawberries, rape,potatoes and tomatoes.

The compounds I and compositions thereof, respectively, are alsosuitable for controlling harmful fungi in the protection of storedproducts or harvest and in the protection of materials. The term“protection of materials” is to be understood to denote the protectionof technical and non-living materials, such as adhesives, glues, wood,paper and paperboard, textiles, leather, paint dispersions, plastics,coiling lubricants, fiber or fabrics, against the infestation anddestruction by harmful microorganisms, such as fungi and bacteria. As tothe protection of wood and other materials, the particular attention ispaid to the following harmful fungi: Ascomycetes such as Ophiostomaspp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp.,Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.;Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllumspp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. andTyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporiumspp., Penicillium spp., Trichorma spp., Alternaria spp., Paecilomycesspp. and Zygomycetes such as Mucor spp., and in addition in theprotection of stored products and harvest the following yeast fungi areworthy of note: Candida spp. and Saccharomyces cerevisae.

The compounds I and compositions thereof, resepectively, may be used forimproving the health of a plant. The invention also relates to a methodfor improving plant health by treating a plant, its propagation materialand/or the locus where the plant is growing or is to grow with aneffective amount of compounds I and compositions thereof, respectively.The term “plant health” is to be understood to denote a condition of theplant and/or its products which is determined by several indicatorsalone or in combination with each other such as yield (e.g. increasedbiomass and/or increased content of valuable ingredients), plant vigor(e.g. improved plant growth and/or greener leaves (“greening effect”)),quality (e.g. improved content or composition of certain ingredients)and tolerance to abiotic and/or biotic stress. The above identifiedindicators for the health condition of a plant may be interdependent ormay result from each other.

The compounds of the formula (I) can be present in different crystalmodifications whose biological activity may differ. They are likewisesubject matter of the present invention.

The compounds I are employed as such or in form of compositions bytreating the fungi or the plants, plant propagation materials, such asseeds, soil, surfaces, materials or rooms to be protected from fungalattack with a fungicidally effective amount of the active substances.The application can be carried out both before and after the infectionof the plants, plant propagation materials, such as seeds, soil,surfaces, materials or rooms by the fungi.

Plant propagation materials may be treated with compounds I as such or acomposition comprising at least one compound I prophylactically eitherat or before planting or transplanting.

The invention also relates to agrochemical compositions comprising anauxiliary and at least one compound I according to the invention.

An agrochemical composition comprises a fungicidally effective amount ofa compound I. The term “effective amount” denotes an amount of thecomposition or of the compounds I, which is sufficient for controllingharmful fungi on cultivated plants or in the protection of materials andwhich does not result in a substantial damage to the treated plants.Such an amount can vary in a broad range and is dependent on variousfactors, such as the fungal species to be controlled, the treatedcultivated plant or material, the climatic conditions and the specificcompound I used.

The compounds I, their N-oxides and salts can be converted intocustomary types of agrochemical compositions, e.g. solutions, emulsions,suspensions, dusts, powders, pastes, granules, pressings, capsules, andmixtures thereof. Examples for composition types are suspensions (e.g.SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW,EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powdersor dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT),granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN),as well as gel formulations for the treatment of plant propagationmaterials such as seeds (e.g. GF). These and further compositions typesare defined in the “Catalogue of pesticide formulation types andinternational coding system”, Technical Monograph No. 2, 6th Ed. May2008, CropLife International.

The compositions are prepared in a known manner, such as described byMollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001;or Knowles, New developments in crop protection product formulation,Agrow Reports DS243, T&F Informa, London, 2005.

Examples for suitable auxiliaries are solvents, liquid carriers, solidcarriers or fillers, surfactants, dispersants, emulsifiers, wetters,adjuvants, solubilizers, penetration enhancers, protective colloids,adhesion agents, thickeners, humectants, repellents, attractants,feeding stimulants, compatibilizers, bactericides, anti-freezing agents,anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents,such as mineral oil fractions of medium to high boiling point, e.g.kerosene, diesel oil; oils of vegetable or animal origin; aliphatic,cyclic and aromatic hydrocarbons, e.g. toluene, paraffin,tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol,propanol, butanol, benzylalcohol, cyclohexanol; glycols; dimethylsulfoxide (DMSO); ketones, e.g. cyclohexanone; esters, e.g. lactates,carbonates, fatty acid esters, gamma-butyrolactone; fatty acids;phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty aciddimethylamides; and mixtures thereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates,silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite,diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate,magnesium oxide; polysaccharide powders, e.g. cellulose, starch;fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas; products of vegetable origin, e.g. cereal meal, treebark meal, wood meal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic,cationic, nonionic and amphoteric surfactants, block polymers,polyelectrolytes, and mixtures thereof. Such surfactants can be used asemusifier, dispersant, solubilizer, wetter, penetration enhancer,protective colloid, or adjuvant. Examples of surfactants are listed inMcCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon'sDirectories, Glen Rock, USA, 2008 (International Ed. or North AmericanEd.).

Suitable anionic surfactants are alkali, alkaline earth or ammoniumsalts of sulfonates, sulfates, phosphates, carboxylates, and mixturesthereof. Examples of sulfonates are alkylarylsulfonates,diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates,sulfonates of fatty acids and oils, sulfonates of ethoxylatedalkylphenols, sulfonates of alkoxylated arylphenols, sulfonates ofcondensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes,sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates orsulfosuccinamates. Examples of sulfates are sulfates of fatty acids andoils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols,or of fatty acid esters. Examples of phosphates are phosphate esters.Examples of carboxylates are alkyl carboxylates, and carboxylatedalcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-substituted fatty acidamides, amine oxides, esters, sugar-based surfactants, polymericsurfactants, and mixtures thereof. Examples of alkoxylates are compoundssuch as alcohols, alkylphenols, amines, amides, arylphenols, fatty acidsor fatty acid esters which have been alkoxylated with 1 to 50equivalents. Ethylene oxide and/or propylene oxide may be employed forthe alkoxylation, preferably ethylene oxide.

Examples of N-substituted fatty acid amides are fatty acid glucamides orfatty acid alkanolamides. Examples of esters are fatty acid esters,glycerol esters or monoglycerides.

Examples of sugar-based surfactants are sorbitans, ethoxylatedsorbitans, sucrose and glucose esters or alkylpolyglucosides. Examplesof polymeric surfactants are home- or copolymers of vinylpyrrolidone,vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for examplequaternary ammonium compounds with one or two hydrophobic groups, orsalts of long-chain primary amines. Suitable amphoteric surfactants arealkylbetains and imidazolines. Suitable block polymers are blockpolymers of the A-B or A-B-A type comprising blocks of polyethyleneoxide and polypropylene oxide, or of the A-B-C type comprising alkanol,polyethylene oxide and polypropylene oxide.

Suitable polyelectrolytes are polyacids or polybases. Examples ofpolyacids are alkali salts of polyacrylic acid or polyacid combpolymers. Examples of polybases are polyvinylamines orpolyethyleneamines.

Suitable adjuvants are compounds, which have a neglectable or even nopesticidal activity themselves, and which improve the biologicalperformance of the compound I on the target.

Examples are surfactants, mineral or vegetable oils, and otherauxilaries. Further examples are listed by Knowles, Adjuvants andadditives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum,carboxymethylcellulose), anorganic clays (organically modified orunmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives suchas alkylisothiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol,urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, andsalts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of lowwater solubility and water-soluble dyes. Examples are inorganiccolorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) andorganic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons,polyvinylacetates, polyvinyl alcohols, polyacrylates, biological orsynthetic waxes, and cellulose ethers.

The agrochemical compositions generally comprise between 0.01 and 95%,preferably between 0.1 and 90%, and most preferably between 0.5 and 75%,by weight of active substance. The active substances are employed in apurity of from 90% to 100%, preferably from 95% to 100% (according toNMR spectrum).

Water-soluble concentrates (LS), Suspoemulsions (SE), flowableconcentrates (FS), powders for dry treatment (DS), water-dispersiblepowders for slurry treatment (WS), water-soluble powders (SS), emulsions(ES), emulsifiable concentrates (EC) and gels (GF) are usually employedfor the purposes of treatment of plant propagation materials,particularly seeds. The compositions in question give, aftertwo-to-tenfold dilution, active substance concentrations of from 0.01 to60% by weight, preferably from 0.1 to 40%, in the ready-to-usepreparations. Application can be carried out before or during sowing.Methods for applying or treating compound I and compositions thereof,respectively, on to plant propagation material, especially seeds includedressing, coating, pelleting, dusting, soaking and in-furrow applicationmethods of the propagation material. Preferably, compound I or thecompositions thereof, respectively, are applied on to the plantpropagation material by a method such that germination is not induced,e.g. by seed dressing, pelleting, coating and dusting.

When employed in plant protection, the amounts of active substancesapplied are, depending on the kind of effect desired, from 0.001 to 2 kgper ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.

In treatment of plant propagation materials such as seeds, e.g. bydusting, coating or drenching seed, amounts of active substance of from0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to100 g and most preferably from 5 to 100 g, per 100 kilogram of plantpropagation material (preferably seed) are generally required.

When used in the protection of materials or stored products, the amountof active substance applied depends on the kind of application area andon the desired effect. Amounts customarily applied in the protection ofmaterials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of activesubstance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, fertilizer, ormicronutrients, and other pesticides (e.g. herbicides, insecticides,fungicides, growth regulators, safeners) may be added to the activesubstances or the compositions comprising them as premix or, ifappropriate not until immediately prior to use (tank mix). These agentscan be admixed with the compositions according to the invention in aweight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The user applies the composition according to the invention usually froma predosage device, a knapsack sprayer, a spray tank, a spray plane, oran irrigation system. Usually, the agrochemical composition is made upwith water, buffer, and/or further auxiliaries to the desiredapplication concentration and the ready-to-use spray liquor or theagrochemical composition according to the invention is thus obtained.Usually, 20 to 2000 liters, preferably 50 to 400 liters, of theready-to-use spray liquor are applied per hectare of agricultural usefularea.

According to one embodiment, individual components of the compositionaccording to the invention such as parts of a kit or parts of a binaryor ternary mixture may be mixed by the user himself in a spray tank andfurther auxiliaries may be added, if appropriate.

Mixing the compounds I or the compositions comprising them in the useform as fungicides with other fungicides results in many cases in anexpansion of the fungicidal spectrum of activity being obtained or in aprevention of fungicide resistance development. Furthermore, in manycases, synergistic effects are obtained.

The following list of active substances, in conjunction with which thecompounds I can be used, is intended to illustrate the possiblecombinations but does not limit them:

A) Respiration inhibitors

-   -   Inhibitors of complex III at Qo site (e.g. strobilurins):        azoxystrobin, coumethoxy-strobin, coumoxystrobin, dimoxystrobin,        enestroburin, fenaminstrobin, fenoxy-strobin/flufenoxystrobin,        fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin,        picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin,        trifloxystrobin,        242-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid        methyl ester and        2-(2-(3-(2,6-di-chlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide,        pyribencarb, triclopyricarb/chlorodincarb, famoxadone,        fenamidone;    -   inhibitors of complex III at Qi site: cyazofamid, amisulbrom,        [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate,        [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate,        [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate,        [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate;    -   inhibitors of complex II (e.g. carboxamides): benodanil,        bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil,        fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin,        penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide,        N-(4′-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide,        N-(2-(1,3,3-trimethyl-butyl)-phenyl)-1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide,        N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide;    -   other respiration inhibitors (e.g. complex I, uncouplers):        diflumetorim,        (5,8-difluoro-quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine;        nitrophenyl derivates: binapacryl, dinobuton, dinocap,        fluazinam; ferimzone; organometal compounds: fentin salts, such        as fentin-acetate, fentin chloride or fentin hydroxide;        ametoctradin; and silthiofam;        B) Sterol biosynthesis inhibitors (SBI fungicides)    -   C₁₄ demethylase inhibitors (DMI fungicides): triazoles:        azaconazole, bitertanol, bromuconazole, cyproconazole,        difenoconazole, diniconazole, diniconazole-M, epoxiconazole,        fenbuconazole, fluquinconazole, flusilazole, flutriafol,        hexaconazole, imibenconazole, ipconazole, metconazole,        myclobutanil, oxpoconazole, paclobutrazole, penconazole,        propiconazole, prothioconazole, simeconazole, tebuconazole,        tetraconazole, triadimefon, triadimenol, triticonazole,        uniconazole; imidazoles: imazalil, pefurazoate, prochloraz,        triflumizol; pyrimidines, pyridines and piperazines: fenarimol,        nuarimol, pyrifenox, triforine;    -   Delta14-reductase inhibitors: aldimorph, dodemorph,        dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin,        piperalin, spiroxamine;    -   Inhibitors of 3-keto reductase: fenhexamid;        C) Nucleic acid synthesis inhibitors    -   phenylamides or acyl amino acid fungicides: benalaxyl,        benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam),        ofurace, oxadixyl;    -   others: hymexazole, octhilinone, oxolinic acid, bupirimate,        5-fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine,        5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine;        D) Inhibitors of cell division and cytoskeleton    -   tubulin inhibitors, such as benzimidazoles, thiophanates:        benomyl, carbendazim, fuberidazole, thiabendazole,        thiophanate-methyl; triazolopyrimidines:        5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine    -   other cell division inhibitors: diethofencarb, ethaboxam,        pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;        E) Inhibitors of amino acid and protein synthesis    -   methionine synthesis inhibitors (anilino-pyrimidines):        cyprodinil, mepanipyrim, pyrimethanil;    -   protein synthesis inhibitors: blasticidin-S, kasugamycin,        kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin,        oxytetracyclin, polyoxine, validamycin A;        F) Signal transduction inhibitors    -   MAP/histidine kinase inhibitors: fluoroimid, iprodione,        procymidone, vinclozolin, fenpiclonil, fludioxonil;    -   G protein inhibitors: quinoxyfen;        G) Lipid and membrane synthesis inhibitors    -   Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos,        pyrazophos, isoprothiolane;    -   lipid peroxidation: dicloran, quintozene, tecnazene,        tolclofos-methyl, biphenyl, chloroneb, etridiazole;    -   phospholipid biosynthesis and cell wall deposition:        dimethomorph, flumorph, mandipropamid, pyrimorph,        benthiavalicarb, iprovalicarb, valifenalate and        N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic        acid-(4-fluorophenyl) ester;    -   compounds affecting cell membrane permeability and fatty acides:        propamocarb, propamocarb-hydrochlorid        H) Inhibitors with Multi Site Action    -   inorganic active substances: Bordeaux mixture, copper acetate,        copper hydroxide, copper oxychloride, basic copper sulfate,        sulfur;    -   thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam,        metiram, propineb, thiram, zineb, ziram;    -   organochlorine compounds (e.g. phthalimides, sulfamides,        chloronitriles): anilazine, chlorothalonil, captafol, captan,        folpet, dichlofluanid, dichlorophen, flusulfamide,        hexachlorobenzene, pentachlorphenole and its salts, phthalide,        tolylfluanid,        N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;    -   guanidines and others: guanidine, dodine, dodine free base,        guazatine, guazatine-acetate, iminoctadine,        iminoctadine-triacetate, iminoctadine-tris(albesilate),        dithianon;        I) Cell wall synthesis inhibitors    -   inhibitors of glucan synthesis: validamycin, polyoxin B; melanin        synthesis inhibitors:    -   pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;        J) Plant defence inducers    -   acibenzolar-5-methyl, probenazole, isotianil, tiadinil,        prohexadione-calcium;    -   phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and        its salts;        K) Unknown mode of action    -   bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet,        debacarb, diclo-mezine, difenzoquat, difenzoquat-methylsulfate,        diphenylamin, fenpyrazamine, flumetover, flusulfamide,        flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl,        oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide,        2-butoxy-6-iodo-3-propylchromen-4-one,        N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl        acetamide,        N′-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl        formamidine,        N′-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl        formamidine,        N′-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl        formamidine,        N′-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl        formamidine,        2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl}-thiazole-4-carboxylic        acid methyl-(1,2,3,4-tetrahydro-naphthalen-1-yl)-amide,        2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazole-1-yl)-acetylFpiperidin-4-yl}-thiazole-4-carboxylic        acid methyl-(R)-1,2,3,4-tetrahydro-naphthalen-1-yl-amide,    -   1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone,        methoxy-acetic acid        6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester,        N-Methyl-2-{1-[(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide,        3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]pyridine,        3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine        (pyrisoxazole), N-(6-methoxy-pyridin-3-yl)cyclopropanecarboxylic        acid amide,        5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzoimidazole,    -   2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;        L) Antifungal biocontrol agents, plant bioactivators:        Ampelomyces quisqualis (e.g. AQ 10® from Intrachem Bio GmbH &        Co. KG, Germany), Aspergillus flavus (e.g. AFLAGUARD® from        Syngenta, CH), Aureobasidium pullulans (e.g. BOTECTOR® from        bio-ferm GmbH, Germany), Bacillus pumilus (e.g. NRRL Accession        No. B-30087 in SONATA® and BALLAD® Plus from AgraQuest Inc.,        USA), Bacillus subtilis (e.g. isolate NRRL-Nr. B-21661 in        RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest Inc.,        USA), Bacillus subtilis var. amyloliquefaciens FZB24 (e.g.        TAEGRO® from Novozyme Biologicals, Inc., USA), Candida oleophila        1-82 (e.g. ASPIRE® from Ecogen Inc., USA), Candida saitoana        (e.g. BIOCURE® (in mixture with lysozyme) and BIOCOAT® from        Micro Flo Company, USA (BASF SE) and Arysta), Chitosan (e.g.        ARMOUR-ZEN from BotriZen Ltd., NZ), Clonostachys rosea f.        catenulata, also named Gliocladium catenulatum (e.g. isolate        J1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans        (e.g. CONTANS® from Prophyta, Germany), Cryphonectria parasitica        (e.g. Endothia parasitica from CNICM, France), Cryptococcus        albidus (e.g. YIELD PLUS® from Anchor Bio-Technologies, South        Africa), Fusarium oxysporum (e.g. BIOFOX® from S.I.A.P.A.,        Italy, FUSACLEAN® from Natural Plant Protection, France),        Metschnikowia fructicola (e.g. SHEMER® from Agrogreen, Israel),        Microdochium dimerum (e.g. ANTIBOT® from Agrauxine, France),        Phlebiopsis gigantea (e.g. ROTSOP® from Verdera, Finland),        Pseudozyma flocculosa (e.g. SPORODEX® from Plant Products Co.        Ltd., Canada), Pythium oligandrum DV74 (e.g. POLYVERSUM® from        Remeslo SSRO, Biopreparaty, Czech Rep.), Reynoutria sachlinensis        (e.g. REGALIA® from Marrone BioInnovations, USA), Talaromyces        flavus V117b (e.g. PROTUS® from Prophyta, Germany), Trichoderma        asperellum SKT-1 (e.g. ECO—HOPE® from Kumiai Chemical Industry        Co., Ltd., Japan), T. atroviride LC52 (e.g. SENTINEL® from        Agrimm Technologies Ltd, NZ), T. harzianum T-22 (e.g.        PLANTSHIELD® der Firma BioWorks Inc., USA), T. harzianum TH 35        (e.g. ROOT PRO® from Mycontrol Ltd., Israel), T. harzianum T-39        (e.g. TRICHODEX® and TRICHODERMA 2000® from Mycontrol Ltd.,        Israel and Makhteshim Ltd., Israel), T. harzianum and T. viride        (e.g. TRICHOPEL from Agrimm Technologies Ltd, NZ), T. harzianum        ICC012 and T. viride ICC080 (e.g. REMEDIER® WP from Isagro        Ricerca, Italy), T. polysporum and T. harzianum (e.g. BINAB®        from BINAB Bio-Innovation AB, Sweden), T. stromaticum (e.g.        TRICOVAB® from C.E.P.L.A.C., Brazil), T. virens GL-21 (e.g.        SOILGARD® from Certis LLC, USA), T. viride (e.g. TRIECO® from        Ecosense Labs. (India) Pvt. Ltd., Indien, BIO-CURE® F from T.        Stanes & Co. Ltd., Indien), T. viride TV1 (e.g. T. viride TV1        from Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (e.g.        BOTRY-ZEN® from Botry-Zen Ltd, NZ);        M) Growth regulators    -   abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine,        brassinolide, butralin, chlormequat (chlormequat chloride),        choline chloride, cyclanilide, daminozide, dikegulac,        dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin,        flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid,        inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide,        mepiquat (mepiquat chloride), naphthaleneacetic acid,        N-6-benzyladenine, paclobutrazol, prohexadione        (prohexadione-calcium), prohydrojasmon, thidiazuron,        triapenthenol, tributyl phosphorotrithioate,        2,3,5-tri-iodobenzoic acid, trinexapac-ethyl and uniconazole;

N) Herbicides

-   -   acetamides: acetochlor, alachlor, butachlor, dimethachlor,        dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor,        napropamide, naproanilide, pethoxamid, pretilachlor, propachlor,        thenylchlor;        -   amino acid derivatives: bilanafos, glyphosate, glufosinate,            sulfosate;        -   aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl,            fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop,            quizalofop, quizalofop-P-tefuryl;        -   Bipyridyls: diquat, paraquat;        -   (thio)carbamates: asulam, butylate, carbetamide,            desmedipham, dimepiperate, eptam (EPTC), esprocarb,            molinate, orbencarb, phenmedipham, prosulfocarb,            pyributicarb, thiobencarb, triallate;        -   cyclohexanediones: butroxydim, clethodim, cycloxydim,            profoxydim, sethoxydim, tepraloxydim, tralkoxydim;        -   dinitroanilines: benfluralin, ethalfluralin, oryzalin,            pendimethalin, prodiamine, trifluralin;        -   diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop,            ethoxyfen, fomesafen, lactofen, oxyfluorfen;        -   hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil;        -   imidazolinones: imazamethabenz, imazamox, imazapic,            imazapyr, imazaquin, imazethapyr;        -   phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic            acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl,            MCPB, Mecoprop;        -   pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet,            norflurazon, pyridate;        -   pyridines: aminopyralid, clopyralid, diflufenican,            dithiopyr, fluridone, fluoroxypyr, picloram, picolinafen,            thiazopyr;        -   sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron,            chlorimuron-ethyl, chlorsulfuron, cinosulfuron,            cyclosulfamuron, ethoxysulfuron, flazasulfuron,            flucetosulfuron, flupyrsulfuron, foramsulfuron,            halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron,            metazosulfuron, metsulfuron-methyl, nicosulfuron,            oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron,            rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron,            triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron,            tritosulfuron,            1-((2-chloro-6-propyl-imidazo[1,2-b]pyridazin-3-yOsulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea;        -   triazines: ametryn, atrazine, cyanazine, dimethametryn,            ethiozin, hexazinone, metamitron, metribuzin, prometryn,            simazine, terbuthylazine, terbutryn, triaziflam;        -   ureas: chlorotoluron, daimuron, diuron, fluometuron,            isoproturon, linuron, metha-benzthiazuron, tebuthiuron;        -   other acetolactate synthase inhibitors: bispyribac-sodium,            cloransulam-methyl, diclosulam, florasulam, flucarbazone,            flumetsulam, metosulam, ortho-sulfamuron, penoxsulam,            propoxycarbazone, pyribambenz-propyl, pyribenzoxim,            pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac,            pyroxasulfone, pyroxsulam;        -   others: amicarbazone, aminotriazole, anilofos, beflubutamid,            benazolin, bencarbazone, benfluresate, benzofenap,            bentazone, benzobicyclon, bicyclopyrone, bromacil,            bromobutide, butafenacil, butamifos, cafenstrole,            carfentrazone, cinidon-ethyl, chlorthal, cinmethylin,            clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat,            diflufenzopyr, Drechslera monoceras, endothal, ethofumesate,            etobenzanid, fenoxasulfone, fentrazamide,            flumiclorac-pentyl, flumioxazin, flupoxam, fluorochloridone,            flurtamone, indanofan, isoxaben, isoxaflutole, lenacil,            propanil, propyzamide, quinclorac, quinmerac, mesotrione,            methyl arsonic acid, naptalam, oxadiargyl, oxadiazon,            oxaziclomefone, pentoxazone, pinoxaden, pyraclonil,            pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate,            quinoclamine, saflufenacil, sulcotrione, sulfentrazone,            terbacil, tefuryltrione, tembotrione, thiencarbazone,            topramezone,            (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2-yloxy)-acetic            acid ethyl ester,            6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid            methyl ester,            6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol,            4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic            acid,            4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carboxylic            acid methyl ester, and            4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2-carboxylic            acid methyl ester.

O) Insecticides

-   -   organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl,        chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon,        dichlorvos, dicrotophos, dimethoate, disulfoton, ethion,        fenitrothion, fenthion, isoxathion, malathion, methamidophos,        methidathion, methyl-parathion, mevinphos, monocrotophos,        oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone,        phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl,        profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos,        triazophos, trichlorfon;    -   carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb,        carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb,        methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb,        triazamate;    -   pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin,        cyphenothrin, cypermethrin, alpha-cypermethrin,        beta-cypermethrin, zeta-cypermethrin, deltamethrin,        esfenvalerate, etofenprox, fenpropathrin, fenvalerate,        imiprothrin, lambda-cyhalothrin, permethrin, prallethrin,        pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate,        tefluthrin, tetramethrin, tralomethrin, transfluthrin,        profluthrin, dimefluthrin;    -   insect growth regulators: a) chitin synthesis inhibitors:        benzoylureas: chlorfluazuron, cyramazin, diflubenzuron,        flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,        teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox,        etoxazole, clofentazine; b) ecdysone antagonists: halofenozide,        methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids:        pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis        inhibitors: spirodiclofen, spiromesifen, spirotetramat;    -   nicotinic receptor agonists/antagonists compounds: clothianidin,        dinotefuran, imidacloprid, thiamethoxam, nitenpyram,        acetamiprid, thiacloprid,        1-(2-chloro-thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1,3,5]triazinane;    -   GABA antagonist compounds: endosulfan, ethiprole, fipronil,        vaniliprole, pyrafluprole, pyriprole,        5-amino-1-(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1H-pyrazole-3-carbothioic        acid amide;    -   macrocyclic lactone insecticides: abamectin, emamectin,        milbemectin, lepimectin, spinosad, spinetoram;    -   mitochondrial electron transport inhibitor (METI) I acaricides:        fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;    -   METI II and III compounds: acequinocyl, fluacyprim,        hydramethylnon;    -   Uncouplers: chlorfenapyr;    -   oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron,        fenbutatin oxide, propargite;    -   moulting disruptor compounds: cryomazine;    -   mixed function oxidase inhibitors: piperonyl butoxide;    -   sodium channel blockers: indoxacarb, metaflumizone;    -   others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl,        pymetrozine, sulfur, thiocyclam, flubendiamide,        chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen,        flupyrazofos, cyflumetofen, amidoflumet, imicyafos,        bistrifluoron, pyrifluquinazon and        1,1′-[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b-trimethyl-1′-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-3,6-diyl]cyclopropaneacetic        acid ester.

The present invention furthermore relates to agrochemical compositionscomprising a mixture of at least one compound I (component 1) and atleast one further active substance useful for plant protection, e.g.selected from the groups A) to O) (component 2), in particular onefurther fungicide, e.g. one or more fungicide from the groups A) to L),as described above, and if desired one suitable solvent or solidcarrier. Those mixtures are of particular interest, since many of themat the same application rate show higher efficiencies against harmfulfungi. Furthermore, combating harmful fungi with a mixture of compoundsI and at least one fungicide from groups A) to L), as described above,is more efficient than combating those fungi with individual compounds Ior individual fungicides from groups A) to L). By applying compounds Itogether with at least one active substance from groups A) to O) asynergistic effect can be obtained, i.e. more then simple addition ofthe individual effects is obtained (synergistic mixtures).

This can be obtained by applying the compounds I and at least onefurther active substance simultaneously, either jointly (e.g. astank-mix) or separately, or in succession, wherein the time intervalbetween the individual applications is selected to ensure that theactive substance applied first still occurs at the site of action in asufficient amount at the time of application of the further activesubstance(s). The order of application is not essential for working ofthe present invention.

In binary mixtures, i.e. compositions according to the inventioncomprising one compound I (component 1) and one further active substance(component 2), e.g. one active substance from groups A) to O), theweight ratio of component 1 and component 2 generally depends from theproperties of the active substances used, usually it is in the range offrom 1:100 to 100:1, regularly in the range of from 1:50 to 50:1,preferably in the range of from 1:20 to 20:1, more preferably in therange of from 1:10 to 10:1 and in particular in the range of from 1:3 to3:1. In ternary mixtures, i.e. compositions according to the inventioncomprising one compound I (component 1) and a first further activesubstance (component 2) and a second further active substance (component3), e.g. two active substances from groups A) to O), the weight ratio ofcomponent 1 and component 2 depends from the properties of the activesubstances used, preferably it is in the range of from 1:50 to 50:1 andparticularly in the range of from 1:10 to 10:1, and the weight ratio ofcomponent 1 and component 3 preferably is in the range of from 1:50 to50:1 and particularly in the range of from 1:10 to 10:1.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group A)(component 2) and particularly selected from azoxystrobin,dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin,picoxystrobin, pyraclostrobin, trifloxystrobin; famoxadone, fenamidone;bixafen, boscalid, fluopyram, fluxapyroxad, isopyrazam, penflufen,penthiopyrad, sedaxane; ametoctradin, cyazofamid, fluazinam, fentinsalts, such as fentin acetate.

Preference is given to mixtures comprising a compound I (component 1)and at least one active substance selected from group B) (component 2)and particularly selected from cyproconazole, difenoconazole,epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole,myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon,triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz,fenarimol, triforine; dodemorph, fenpropimorph, tridemorph, fenpropidin,spiroxamine; fenhexamid.

Preference is given to mixtures comprising a compound I (component 1)and at least one active substance selected from group C) (component 2)and particularly selected from metalaxyl, (metalaxyl-M) mefenoxam,ofurace.

Preference is given to mixtures comprising a compound I (component 1)and at least one active substance selected from group D) (component 2)and particularly selected from benomyl, carbendazim, thiophanate-methyl,ethaboxam, fluopicolide, zoxamide, metrafenone, pyriofenone.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group E)(component 2) and particularly selected from cyprodinil, mepanipyrim,pyrimethanil.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group F)(component 2) and particularly selected from iprodione, fludioxonil,vinclozolin, quinoxyfen.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group G)(component 2) and particularly selected from dimethomorph, flumorph,iprovalicarb, benthiavalicarb, mandipropamid, propamocarb.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group H)(component 2) and particularly selected from copper acetate, copperhydroxide, copper oxychloride, copper sulfate, sulfur, mancozeb,metiram, propineb, thiram, captafol, folpet, chlorothalonil,dichlofluanid, dithianon.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group I)(component 2) and particularly selected from carpropamid and fenoxanil.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group J)(component 2) and particularly selected from acibenzolar-5-methyl,probenazole, tiadinil, fosetyl, fosetyl-aluminium, H₃PO₃ and saltsthereof.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group K)(component 2) and particularly selected from cymoxanil, proquinazid andN-methyl-2-{1-[(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group L)(component 2) and particularly selected from Bacillus subtilis strainNRRL No. B-21661, Bacillus pumilus strain NRRL No. B-30087 andUlocladium oudemansii.

Accordingly, the present invention furthermore relates to compositionscomprising one compound I (component 1) and one further active substance(component 2), which further active substance is selected from thecolumn “Component 2” of the lines D-1 to D-370 of Table D.

A further embodiment relates to the compositions D-1 to D-370 listed inTable D, where a row of Table D corresponds in each case to a fungicidalcomposition comprising one of the in the present specificationindividualized compounds of formula I (component 1) and the respectivefurther active substance from groups A) to O) (component 2) stated inthe row in question.

Preferably, the compositions described comprise the active substances insynergistically effective amounts.

TABLE D Composition comprising one indiviualized compound I and onefurther active substance from groups A) to O) Mixture Component 1Component 2 D-1 one individualized compound I Azoxystrobin D-2 oneindividualized compound I Coumethoxystrobin D-3 one individualizedcompound I Coumoxystrobin D-4 one individualized compound IDimoxystrobin D-5 one individualized compound I Enestroburin D-6 oneindividualized compound I Fenaminstrobin D-7 one individualized compoundI Fenoxystrobin/Flufenoxystrobin D-8 one individualized compound IFluoxastrobin D-9 one individualized compound I Kresoxim-methyl D-10 oneindividualized compound I Metominostrobin D-11 one individualizedcompound I Orysastrobin D-12 one individualized compound I PicoxystrobinD-13 one individualized compound I Pyraclostrobin D-14 oneindividualized compound I Pyrametostrobin D-15 one individualizedcompound I Pyraoxystrobin D-16 one individualized compound I PyribencarbD-17 one individualized compound I Trifloxystrobin D-18 oneindividualized compound I Triclopyricarb/Chlorodincarb D-19 oneindividualized compound I 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester D-20 one individualizedcompound I 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)- 2-methoxyimino-N-methyl-acetamideD-21 one individualized compound I Benalaxyl D-22 one individualizedcompound I Benalaxyl-M D-23 one individualized compound I Benodanil D-24one individualized compound I Benzovindiflupyr D-25 one individualizedcompound I Bixafen D-26 one individualized compound I Boscalid D-27 oneindividualized compound I Carboxin D-28 one individualized compound IFenfuram D-29 one individualized compound I Fenhexamid D-30 oneindividualized compound I Flutolanil D-31 one individualized compound IFluxapyroxad D-32 one individualized compound I Furametpyr D-33 oneindividualized compound I Isopyrazam D-34 one individualized compound IIsotianil D-35 one individualized compound I Kiralaxyl D-36 oneindividualized compound I Mepronil D-37 one individualized compound IMetalaxyl D-38 one individualized compound I Metalaxyl-M D-39 oneindividualized compound I Ofurace D-40 one individualized compound IOxadixyl D-41 one individualized compound I Oxycarboxin D-42 oneindividualized compound I Penflufen D-43 one individualized compound IPenthiopyrad D-44 one individualized compound I Sedaxane D-45 oneindividualized compound I Tecloftalam D-46 one individualized compound IThifluzamide D-47 one individualized compound I Tiadinil D-48 oneindividualized compound I 2-Amino-4-methyl-thiazole-5- carboxylic acidanilide D-49 one individualized compound IN-(4′-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole- 4-carboxamide D-50 oneindividualized compound I N-(2-(1,3,3-trimethyl-butyl)-phenyl)-1,3-dimethyl-5-fluoro-1H-pyrazole- 4-carboxamide D-51 one individualizedcompound I 3-(difluoromethyl)-1-methyl-N-(1,1,3-tri-methylindan-4-yl)pyrazole-4-carbox- amide D-52 one individualizedcompound I 3-(trifluoromethyl)-1-methyl-N-(1,1,3-tri-methylindan-4-yl)pyrazole-4-carbox- amide D-53 one individualizedcompound I 1,3-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide D-54 one individualized compound I3-(trifluoromethyl)-1,5-dimethyl- N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide D-55 one individualized compound I3-(difluoromethyl)-1,5-dimethyl- N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide D-56 one individualized compound I1,3,5-trimethyl-N-(1,1,3-trimethylindan- 4-yl)pyrazole-4-carboxamideD-57 one individualized compound I Dimethomorph D-58 one individualizedcompound I Flumorph D-59 one individualized compound I Pyrimorph D-60one individualized compound I Flumetover D-61 one individualizedcompound I Fluopicolide D-62 one individualized compound I FluopyramD-63 one individualized compound I Zoxamide D-64 one individualizedcompound I Carpropamid D-65 one individualized compound I DiclocymetD-66 one individualized compound I Mandipropamid D-67 one individualizedcompound I Oxytetracyclin D-68 one individualized compound I SilthiofamD-69 one individualized compound I N-(6-methoxy-pyridin-3-yl)cyclopropanecarboxylic acid amide D-70 one individualized compound IAzaconazole D-71 one individualized compound I Bitertanol D-72 oneindividualized compound I Bromuconazole D-73 one individualized compoundI Cyproconazole D-74 one individualized compound I Difenoconazole D-75one individualized compound I Diniconazole D-76 one individualizedcompound I Diniconazole-M D-77 one individualized compound IEpoxiconazole D-78 one individualized compound I Fenbuconazole D-79 oneindividualized compound I Fluquinconazole D-80 one individualizedcompound I Flusilazole D-81 one individualized compound I FlutriafolD-82 one individualized compound I Hexaconazol D-83 one individualizedcompound I Imibenconazole D-84 one individualized compound I IpconazoleD-85 one individualized compound I Metconazole D-86 one individualizedcompound I Myclobutanil D-87 one individualized compound I OxpoconazolD-88 one individualized compound I Paclobutrazol D-89 one individualizedcompound I Penconazole D-90 one individualized compound I PropiconazoleD-91 one individualized compound I Prothioconazole D-92 oneindividualized compound I Simeconazole D-93 one individualized compoundI Tebuconazole D-94 one individualized compound I Tetraconazole D-95 oneindividualized compound I Triadimefon D-96 one individualized compound ITriadimenol D-97 one individualized compound I Triticonazole D-98 oneindividualized compound I Uniconazole D-99 one individualized compound I1-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1H-[1,2,4]triazole, D-100 one individualized compound I2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]- 2H-[1,2,4]triazole-3-thiol D-101one individualized compound I Cyazofamid D-102 one individualizedcompound I Amisulbrom D-103 one individualized compound I Imazalil D-104one individualized compound I Imazalil-sulfate D-105 one individualizedcompound I Pefurazoate D-106 one individualized compound I ProchlorazD-107 one individualized compound I Triflumizole D-108 oneindividualized compound I Benomyl D-109 one individualized compound ICarbendazim D-110 one individualized compound I Fuberidazole D-111 oneindividualized compound I Thiabendazole D-112 one individualizedcompound I Ethaboxam D-113 one individualized compound I EtridiazoleD-114 one individualized compound I Hymexazole D-115 one individualizedcompound I 2-(4-Chloro-phenyl)-N-[4-(3,4-di-methoxy-phenyl)-isoxazol-5-yl]-2- prop-2-yn-yloxy-acetamide D-116 oneindividualized compound I Fluazinam D-117 one individualized compound IPyrifenox D-118 one individualized compound I3-[5-(4-Chloro-phenyl)-2,3-dimethyl- isoxazolidin-3-yl]-pyridine(Pyrisoxazole) D-119 one individualized compound I3-[5-(4-Methyl-phenyl)-2,3-dimethyl- isoxazolidin-3-yl]-pyridine D-120one individualized compound I Bupirimate D-121 one individualizedcompound I Cyprodinil D-122 one individualized compound I5-Fluorocytosine D-123 one individualized compound I5-Fluoro-2-(p-tolylmethoxy)pyrimidin- 4-amine D-124 one individualizedcompound I 5-Fluoro-2-(4-fluorophenylmethoxy)- pyrimidin-4-amine D-125one individualized compound I Diflumetorim D-126 one individualizedcompound I (5,8-Difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)- phenyl]-ethyl}-amine D-127 oneindividualized compound I Fenarimol D-128 one individualized compound IFerimzone D-129 one individualized compound I Mepanipyrim D-130 oneindividualized compound I Nitrapyrin D-131 one individualized compound INuarimol D-132 one individualized compound I Pyrimethanil D-133 oneindividualized compound I Triforine D-134 one individualized compound IFenpiclonil D-135 one individualized compound I Fludioxonil D-136 oneindividualized compound I Aldimorph D-137 one individualized compound IDodemorph D-138 one individualized compound I Dodemorph-acetate D-139one individualized compound I Fenpropimorph D-140 one individualizedcompound I Tridemorph D-141 one individualized compound I FenpropidinD-142 one individualized compound I Fluoroimid D-143 one individualizedcompound I Iprodione D-144 one individualized compound I ProcymidoneD-145 one individualized compound I Vinclozolin D-146 one individualizedcompound I Famoxadone D-147 one individualized compound I FenamidoneD-148 one individualized compound I Flutianil D-149 one individualizedcompound I Octhilinone D-150 one individualized compound I ProbenazoleD-151 one individualized compound I Fenpyrazamine D-152 oneindividualized compound I Acibenzolar-S-methyl D-153 one individualizedcompound I Ametoctradin D-154 one individualized compound I AmisulbromD-155 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[(3-iso-butyryloxymethoxy-4-methoxypyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo- [1,5]dioxonan-7-yl]2-methylpropanoate D-156 one individualized compound I[(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate D-157 oneindividualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo- 1,5-dioxonan-7-yl]2-methylpropanoate D-158 one individualized compound I[(3S,6S,7R,8R)-8-benzyl-3-[(3- isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo- 1,5-dioxonan-7-yl]2-methylpropanoate D-159 one individualized compound I[(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyri-dine-2-carbonyl]amino]-6-methyl-4,9- dioxo-1,5-dioxonan-7-yl]2-methylpropanoate D-160 one individualized compound I(3S,6S,7R,8R)-3-[[(3-hydroxy-4- methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)- 1,5-dioxonan-7-yl2-methylpropanoate D-161 one individualized compound I Anilazin D-162one individualized compound I Blasticidin-S D-163 one individualizedcompound I Captafol D-164 one individualized compound I Captan D-165 oneindividualized compound I Chinomethionat D-166 one individualizedcompound I Dazomet D-167 one individualized compound I Debacarb D-168one individualized compound I Diclomezine D-169 one individualizedcompound I Difenzoquat, D-170 one individualized compound IDifenzoquat-methylsulfate D-171 one individualized compound I FenoxanilD-172 one individualized compound I Folpet D-173 one individualizedcompound I Oxolinsaure D-174 one individualized compound I PiperalinD-175 one individualized compound I Proquinazid D-176 one individualizedcompound I Pyroquilon D-177 one individualized compound I QuinoxyfenD-178 one individualized compound I Triazoxid D-179 one individualizedcompound I Tricyclazole D-180 one individualized compound I2-Butoxy-6-iodo-3-propyl-chromen-4- one D-181 one individualizedcompound I 5-Chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzoimidazole D-182 one individualized compound I5-Chloro-7-(4-methyl-piperidin-1-yl)-6-(2,4,6-trifluoro-phenyl)-[1,2,4]tri- azolo[1,5-a]pyrimidine D-183 oneindividualized compound I Ferbam D-184 one individualized compound IMancozeb D-185 one individualized compound I Maneb D-186 oneindividualized compound I Metam D-187 one individualized compound IMethasulphocarb D-188 one individualized compound I Metiram D-189 oneindividualized compound I Propineb D-190 one individualized compound IThiram D-191 one individualized compound I Zineb D-192 oneindividualized compound I Ziram D-193 one individualized compound IDiethofencarb D-194 one individualized compound I Benthiavalicarb D-195one individualized compound I Iprovalicarb D-196 one individualizedcompound I Propamocarb D-197 one individualized compound I Propamocarbhydrochlorid D-198 one individualized compound I Valifenalate D-199 oneindividualized compound I N-(1-(1-(4-cyanophenyl)ethane-sulfonyl)-but-2-yl) carbamic acid- (4-fluorophenyl) ester D-200 oneindividualized compound I Dodine D-201 one individualized compound IDodine free base D-202 one individualized compound I Guazatine D-203 oneindividualized compound I Guazatine-acetate D-204 one individualizedcompound I Iminoctadine D-205 one individualized compound IIminoctadine-triacetate D-206 one individualized compound IIminoctadine-tris(albesilate) D-207 one individualized compound IKasugamycin D-208 one individualized compound IKasugamycin-hydrochloride-hydrate D-209 one individualized compound IPolyoxine D-210 one individualized compound I Streptomycin D-211 oneindividualized compound I Validamycin A D-212 one individualizedcompound I Binapacryl D-213 one individualized compound I Dicloran D-214one individualized compound I Dinobuton D-215 one individualizedcompound I Dinocap D-216 one individualized compound INitrothal-isopropyl D-217 one individualized compound I Tecnazen D-218one individualized compound I Fentin salts D-219 one individualizedcompound I Dithianon D-220 one individualized compound I2,6-dimethyl-1H,5H-[1,4]dithiino [2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetraone D-221 one individualized compound IIsoprothiolane D-222 one individualized compound I Edifenphos D-223 oneindividualized compound I Fosetyl, Fosetyl-aluminium D-224 oneindividualized compound I Iprobenfos D-225 one individualized compound IPhosphorous acid (H₃PO₃) and derivatives D-226 one individualizedcompound I Pyrazophos D-227 one individualized compound ITolclofos-methyl D-228 one individualized compound I ChlorothalonilD-229 one individualized compound I Dichlofluanid D-230 oneindividualized compound I Dichlorophen D-231 one individualized compoundI Flusulfamide D-232 one individualized compound I HexachlorbenzeneD-233 one individualized compound I Pencycuron D-234 one individualizedcompound I Pentachlorophenol and salts D-235 one individualized compoundI Phthalide D-236 one individualized compound I Quintozene D-237 oneindividualized compound I Thiophanate Methyl D-238 one individualizedcompound I Tolylfluanid D-239 one individualized compound IN-(4-chloro-2-nitro-phenyl)-N-ethyl- 4-methyl-benzenesulfonamide D-240one individualized compound I Bordeaux mixture D-241 one individualizedcompound I Copper acetate D-242 one individualized compound I Copperhydroxide D-243 one individualized compound I Copper oxychloride D-244one individualized compound I basic Copper sulfate D-245 oneindividualized compound I Sulfur D-246 one individualized compound IBiphenyl D-247 one individualized compound I Bronopol D-248 oneindividualized compound I Cyflufenamid D-249 one individualized compoundI Cymoxanil D-250 one individualized compound I Diphenylamin D-251 oneindividualized compound I Metrafenone D-252 one individualized compoundI Pyriofenone D-253 one individualized compound I Mildiomycin D-254 oneindividualized compound I Oxin-copper D-255 one individualized compoundI Oxathiapiprolin D-256 one individualized compound I Prohexadionecalcium D-257 one individualized compound I Spiroxamine D-258 oneindividualized compound I Tebufloquin D-259 one individualized compoundI Tolylfluanid D-260 one individualized compound IN-(Cyclopropylmethoxyimino-(6- difluoromethoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide D-261 one individualized compound IN′-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine D-262 oneindividualized compound I N′-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine D-263 oneindividualized compound I N′-(2-methyl-5-trifluoromethyl-4-(3-tri-methylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine D-264 oneindividualized compound I N′-(5-difluoromethyl-2-methyl-4-(3-tri-methylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine D-265 oneindividualized compound I Methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester D-266 one individualizedcompound I Bacillus subtilis NRRL No. B-21661 D-267 one individualizedcompound I Bacillus pumilus NRRL No. B-30087 D-268 one individualizedcompound I Ulocladium oudemansii D-269 one individualized compound ICarbaryl D-270 one individualized compound I Carbofuran D-271 oneindividualized compound I Carbosulfan D-272 one individualized compoundI Methomylthiodicarb D-273 one individualized compound I BifenthrinD-274 one individualized compound I Cyfluthrin D-275 one individualizedcompound I Cypermethrin D-276 one individualized compound Ialpha-Cypermethrin D-277 one individualized compound I zeta-CypermethrinD-278 one individualized compound I Deltamethrin D-279 oneindividualized compound I Esfenvalerate D-280 one individualizedcompound I Lambda-cyhalothrin D-281 one individualized compound IPermethrin D-282 one individualized compound I Tefluthrin D-283 oneindividualized compound I Diflubenzuron D-284 one individualizedcompound I Flufenoxuron D-285 one individualized compound I LufenuronD-286 one individualized compound I Teflubenzuron D-287 oneindividualized compound I Spirotetramate D-288 one individualizedcompound I Clothianidin D-289 one individualized compound I DinotefuranD-290 one individualized compound I Imidacloprid D-291 oneindividualized compound I Thiamethoxam D-292 one individualized compoundI Flupyradifurone D-293 one individualized compound I Acetamiprid D-294one individualized compound I Thiacloprid D-295 one individualizedcompound I Endosulfan D-296 one individualized compound I Fipronil D-297one individualized compound I Abamectin D-298 one individualizedcompound I Emamectin D-299 one individualized compound I Spinosad D-300one individualized compound I Spinetoram D-301 one individualizedcompound I Hydramethylnon D-302 one individualized compound IChlorfenapyr D-303 one individualized compound I Fenbutatin oxide D-304one individualized compound I Indoxacarb D-305 one individualizedcompound I Metaflumizone D-306 one individualized compound I FlonicamidD-307 one individualized compound I Lubendiamide D-308 oneindividualized compound I Chlorantraniliprole D-309 one individualizedcompound I Cyazypyr (HGW86) D-310 one individualized compound ICyflumetofen D-311 one individualized compound I Acetochlor D-312 oneindividualized compound I Dimethenamid D-313 one individualized compoundI metolachlor D-314 one individualized compound I Metazachlor D-315 oneindividualized compound I Glyphosate D-316 one individualized compound IGlufosinate D-317 one individualized compound I Sulfosate D-318 oneindividualized compound I Clodinafop D-319 one individualized compound IFenoxaprop D-320 one individualized compound I Fluazifop D-321 oneindividualized compound I Haloxyfop D-322 one individualized compound IParaquat D-323 one individualized compound I Phenmedipham D-324 oneindividualized compound I Clethodim D-325 one individualized compound ICycloxydim D-326 one individualized compound I Profoxydim D-327 oneindividualized compound I Sethoxydim D-328 one individualized compound ITepraloxydim D-329 one individualized compound I Pendimethalin D-330 oneindividualized compound I Prodiamine D-331 one individualized compound ITrifluralin D-332 one individualized compound I Acifluorfen D-333 oneindividualized compound I Bromoxynil D-334 one individualized compound IImazamethabenz D-335 one individualized compound I Imazamox D-336 oneindividualized compound I Imazapic D-337 one individualized compound IImazapyr D-338 one individualized compound I Imazaquin D-339 oneindividualized compound I Imazethapyr D-340 one individualized compoundI 2,4-Dichlorophenoxyacetic acid (2,4-D) D-341 one individualizedcompound I Chloridazon D-342 one individualized compound I ClopyralidD-343 one individualized compound I Fluroxypyr D-344 one individualizedcompound I Picloram D-345 one individualized compound I PicolinafenD-346 one individualized compound I Bensulfuron D-347 one individualizedcompound I Chlorimuron-ethyl D-348 one individualized compound ICyclosulfamuron D-349 one individualized compound I Iodosulfuron D-350one individualized compound I Mesosulfuron D-351 one individualizedcompound I Metsulfuron-methyl D-352 one individualized compound INicosulfuron D-353 one individualized compound I Rimsulfuron D-354 oneindividualized compound I Triflusulfuron D-355 one individualizedcompound I Atrazine D-356 one individualized compound I Hexazinone D-357one individualized compound I Diuron D-358 one individualized compound IFlorasulam D-359 one individualized compound I Pyroxasulfone D-360 oneindividualized compound I Bentazone D-361 one individualized compound ICinidon-ethyl D-362 one individualized compound I Cinmethylin D-363 oneindividualized compound I Dicamba D-364 one individualized compound IDiflufenzopyr D-365 one individualized compound I Quinclorac D-366 oneindividualized compound I Quinmerac D-367 one individualized compound IMesotrione D-368 one individualized compound I Saflufenacil D-369 oneindividualized compound I Topramezone D-370 one individualized compoundI 1,1′-[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]-1,3,4,4a,5,6,6a,12,12a,12b-deca-hydro- 12-hydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naph-tho[2,1-b]pyrano[3,4-e]pyran-3,6-diyl] cyclopropaneacetic acid ester

The active substances referred to as component 2, their preparation andtheir activity against harmful fungi is known (cf.:http://www.alanwood.net/pesticides/); these substances are commerciallyavailable. The compounds described by IUPAC nomenclature, theirpreparation and their fungicidal activity are also known (cf. Can. J.Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031; EP-A 226917; EP-A 243 970; EP-A 256 503; EP-A 428 941; EP-A 532 022; EP-A 1 028125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE19650197; DE 10021412; DE 102005009458; U.S. Pat. No. 3,296,272; U.S.Pat. No. 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783;WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO02/22583; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO06/87343; WO 07/82098; WO 07/90624, WO 11/028,657).

The mixtures of active substances can be prepared as compositionscomprising besides the active ingredients at least one inert ingredientby usual means, e.g. by the means given for the compositions ofcompounds I.

Concerning usual ingredients of such compositions reference is made tothe explanations given for the compositions containing compounds I.

The mixtures of active substances according to the present invention aresuitable as fungicides, as are the compounds of formula I. They aredistinguished by an outstanding effectiveness against a broad spectrumof phytopathogenic fungi, especially from the classes of theAscomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn.Oomycetes). In addition, it is referred to the explanations regardingthe fungicidal activity of the compounds and the compositions containingcompounds I, respectively.

I. SYNTHESIS EXAMPLES

With appropriate modification of the starting materials, the proceduresgiven in the synthesis examples below were used to obtain furthercompounds I. The compounds produced in this manner are listed in Table Vbelow including corresponding physical data.2-(2-Chloro-4-hydroxyphenyl)ethylamine-tert-butylcarbamate was preparedas described in WO 2004026305 A1. 2-(2-Fluoro-4-methoxyphenyl)ethylaminehydrochloride was prepared from 2-fluoro-4-methoxybenzaldehyde asdescribed in US 20110054173 A1.2-(3-Methoxy-4-hydroxyphenyl)ethylamine-tert-butylcarbamate was preparedaccording to literature precedents in Bioorganic & Medicinal Chemistry(2011), 19(2), 783-788 and in European Journal of Medicinal Chemistry(2008), 43(6), 1160-1170. 6-Dichloro-5-pyrimidinecarboxylic acid methylester was prepared from 4,6-dihydroxypyrimidine as described in Journalof Medicinal Chemistry (2010), 53(13), 5012-5024.

Example 1 Preparation of2-(2-fluoro-4-hydroxyphenyl)ethylamine-tert-butyl carbamate

2-(2-Fluoro-4-methoxyphenyl)ethylamine hydrochloride (270 g, 1.6 mol)was carefully added portionwise to 48% HBr (1.5 L) and stirred for 4 hat 140° C. The reaction solution was reduced in vacuo, then acetonitrile(1 L) was added to the residue and was evaporated to dryness. The crudeproduct was stirred in diisopropylether and recovered by filtration toafford 222 g (940 mmol, 59%) of desired phenol. The purified phenol wasdissolved in dichloromethane (DCM, 1.5 L) to which was addedtriethylamine (275 mL), tert-butyloxycarbonyl anhydride (215 g, 990mmol) in a solution of DCM (500 mL), and was stirred for 30 min at roomtemperature. The reaction solution was washed with water, dried overNa₂SO₄ and then concentrated in vacuo. The residue was purified by flashsilica column chromatography (4:1 cyclohexane:MTBE) to afford 220 g (860mmol, 92%) of 2-(2-Fluoro-4-hydroxyphenyl)ethylamine-tert-butylcarbamate.

Example 2 Preparation of2-[4-[[2-(trifluoromethyl)-4-pyridyl]oxy]phenyl]ethanamine hydrochloride

To a solution of N-tert-butyloxy-carbonyl-protected tyramine (130 g, 550mmol), potassium carbonate (76 g, 550 mmol) and catalytic amounts ofpotassium iodide in N-methyl-2-pyrrolidone (NMP, 400 mL) that wasstirred for 10 minutes at room temperature was added4-chloro-2-trifluoromethylpyridine (100 g, 550 mmol). The reactionmixture was then heated to 160° C. for 6 h, cooled, poured into waterand extracted with methyl tert-butylether (MTBE, 3×). The combinedorganic layers were washed with succesivly with 3 N NaOH and water,dried over Na₂SO₄, and reduced in vacuo. The crude residue was purifiedby flash silica gel column chromatography to afford a 48% (102 g, 265mmol) yield of N-tert-butyloxycarbonyl-protected2-[4-[[2-(trifluoromethyl)-4-pyridyl]oxy]phenyl]ethanamine. To asolution of this material in dioxane (200 mL) was added 4 M HCl indioxane (250 mL). The solution was left overnight to stir at roomtemperature, which resulted in precipitation of2-[4-[[2-(trifluoromethyl)-4-pyridyl]oxy]phenyl]ethanamine. The reactionsolution was evaporated and the residue was stirred with pentane andfiltered to provide 100% (37 g, 104 mmol) of the desired aminehydrochloride.

Example 3 Preparation of6-chloro-N42-[4-(6-chloro-5-methoxy-pyrimidin-4-yl)oxyphenyl]ethyl]-5-methoxy-pyrimidin-4-amine(V-17)

To a solution of 4-hydroxyphenylethylamine hydrochloride (300 mg) inN,N-dimethyl formamide (DMF, 5 mL) was added diisopropylethylamine (355mg, 2 equiv.). The solution was stirred for 5 min before the addition of4,6-dichloro-5-methoxypyrimidine (249 mg, 1 equiv.). The reactionmixture was then stirred for 16 h at room temperature before it wasconcentrated in vacuo. The residue was dissolved in DMF (10 mL) and wasstirred with sodium hydride (66 mg, 2.2 equiv.) for 20 min at roomtemperature. Another portion of 4,6-dichloro-5-methoxypyrimidine (269mg, 1.2 equiv.) was introduced into the reaction mixture, which was thenleft to stir at room temperature for 48 h. The DMF was then removed invacuo and the product was purified by flash silica column chromatographyto afford 178 mg (31% yield) of the product as a white solid.

Example 4 Preparation of6-chloro-N-[2-[2-fluoro-4-[[4-(trifluoromethyl)-2-pyridyl]oxy]phenyl]ethyl]-5-methoxy-pyrimidin-4-amine(V-3)

To a solution of2-[2-fluoro-4-[[4-(trifluoromethyl)-2-pyridyl]oxy]phenyl]ethanaminehydrochloride (378 mg, 1 mmol) in N-methyl-2-pyrrolidone (5 mL) wasadded diisopropylethylamine (0.4 mL, 2.3 mmol). The solution was stirredfor 5 min at room temperature at which time4,6-dichloro-5-methylpyrimidine (150 mg, 0.8 mmol) was added. Thereaction mixture was stirred at 80° C. overnight then allowed to cool toroom temperature. Water was added and was extracted with MTBE (3×). Thecombined organic layers were washed with water, dried over Na₂SO₄, andconcentrated in vacuo. The residue was purified by flash silica columnchromatography to provide 330 mg (0.80 mmol, 84%) of the light yellowsolid product.

The compounds listed in Table V have been prepared in an analogousmanner.

TABLE V Compounds V-1 to V-49 of formula I.A as defined above andwherein R¹ and R² in each case are hydrogen. ex. HPLC m.p. no R^(a2)R^(a5) R^(a6) Het R X (R^(b))_(n)* R_(t) (min) (° C.) V-1 H Cl Cl H-1 H—CH₂— n = 0 3.999 89 V-2 H H Cl H-1 H —CH₂— n = 0 3.568 135 V-3 H Me ClH-1 H —CH₂— o-F; n = 1 1.289 121 V-4 H OMe Cl H-1 H —CH₂— o-F; n = 11.297 95 V-5 H COOMe Cl H-2 H —CH₂— n = 0 1.316 V-6 H COOMe Cl H-2 H—CH₂— o-F; n = 1 1.326 112 V-7 H Cl Cl H-1 H —CH₂— o-F; n = 1 1.364 97V-8 H Cl Cl H-1 H —CH₂— m-OMe; n = 1 1.35 V-9 H Me Cl H-2 H —CH₂— o-F; n= 1 1.221 V-10 H F Cl H-1 H —CH₂— o-F; n = 1 1.332 142 V-11 H F Cl H-2 H—CH₂— o-F; n = 1 1.278 116 V-12 H Br F H-1 H —CH₂— o-F; n = 1 1.361 V-13H Me Cl H-1 H —CH₂— m-Cl; n = 1 1.317 120 V-14 H OMe Cl H-1 Me —CH₂—o-F; n = 1 1.373 V-15 H CN Cl H-1 H —CH₂— n = 0 1.34 105 V-16 H OMe ClH-1 H —CH₂— m-OMe; n = 1 1.231 106 V-17 H OMe Cl H-28 H —CH₂— n = 01.157 123 V-18 H OMe Cl H-7 H —CH₂— n = 0 1.11 125 V-19 H OMe Cl H-1 H—CH₂— n = 0 1.27 V-20 H OMe Cl H-2 H —CH₂— m-OMe; n = 1 1.21 V-21 H OMeCl H-2 H —CH₂— n = 0 1.22 V-22 H OMe Cl H-6 H —CH₂— n = 0 1.1 105 V-23 HOMe Cl H-1 H —CH(CH₂OH)— n = 0 1.169 V-24 H Me Cl H-1 H —CH(CH₂OH)— n =0 1.142 V-25 Me Cl Cl H-1 H —CH₂— o-F; n = 1 1.432 108 V-26 Me Me Cl H-1H —CH₂— o-F; n = 1 1.172 V-27 H OMe Cl H-1 Me —CH₂— o-F, n = 1 1.373V-28 H Me Cl H-30 H —CH₂— n = 0 1.173 162 V-29 H CN Cl H-1 H —CH₂— o-F;n = 1 1.34 184 V-30 H Cl Cl H-2 H —CH(CH₃)— n = 0 1.36 150 V-31 H Br ClH-1 H —CH₂— o-F; n = 1 1.403 V-32 H COOMe Cl H-1 H —CH₂— o-F; n = 1 1.37V-33 Cl Cl Cl H-1 H —CH₂— o-F; n = 1 1.468 V-34 H Et Cl H-1 H —CH₂— m-F;n = 1 1.338 V-35 H Et Cl H-2 H —CH₂— m-F; n = 1 1.294 130 V-36 H Br ClH-2 H —CH₂— o-F; n = 1 1.354 132 V-37 H Me Cl H-1 H —CH₂— m-Me; n = 11.278 130 V-38 Me Me Cl H-2 H —CH₂— o-F; n = 1 1.140 141 V-39 Me C(CH₃)₃Cl H-1 H —CH₂— o-F; n = 1 1.238 V-40 Me C(CH₃)₃ Cl H-2 H —CH₂— o-F; n =1 1.199 V-41 H Et Cl 6-chloro- H —CH₂— n = 0 1.291 116 5-ethyl-pyrimidin- 4-yl V-42 NH₂ H Cl H-1 H —CH₂— o-F; n = 1 1.052 V-43 Me H ClH-1 H —CH₂— o-F; n = 1 1.208 V-44 H Me Cl H-1 H —CH₂— m-F; n = 1 1.252126 V-45 H Me Cl H-7 H —CH₂— n = 0 1.09 139 V-46 H Me Cl H-8 H —CH₂— n =0 1.07 V-47 H Cl Cl H-1 H —CH(CH₂OH)— n = 0 1.228 V-48 H OMe Cl H-1 H—CH(COOMe)— n = 0 1.310 V-49 H Me Cl H-1 H —CH(CH₂OCH₃)— n = 0 1.293 87*The position of R^(b) on the phenyl ring is defined relative to theCR¹R²-moiety bound to the phenyl ring as being in ortho (o-) or meta(m-) position. n = 0 indicates that no substituent R^(b) is present onthe phenyl ring. m.p. = melting point (° C.). HPLC-MS: HPLC-columnKinetex XB C18 1.7μ (50 × 2.1 mm); eluent: acetonitrile/water + 0.1% TFA(gradient from 5:95 to 100:0 in 1.5 min at 60° C., flow gradient from0.8 to 1.0 ml/min in 1.5 min). MS: Quadrupol Electrospray Ionisation, 80V (positive mode).

II. BIOLOGICAL EXAMPLES FOR FUNGICIDAL ACTIVITY

The fungicidal action of the compounds I was demonstrated by thefollowing experiments:

A. Glass House Trials

The spray solutions were prepared in several steps: The stock solutionwere prepared: a mixture of acetone and/or dimethylsulfoxide and thewetting agent/emulsifier Wettol, which is based on ethoxylatedalkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 wasadded to 25 mg of the compound to give a total of 5 ml. Water was thenadded to total volume of 100 ml.

This stock solution was diluted with the describedsolvent-emulsifier-water mixture to the given concentration.

After the final cultivation period, the extent of fungal attack on theleaves was visually assessed as % diseased leaf area.

Use Example 1: Protective Control of Soy Bean Rust on Soy Beans Causedby Phakopsora Pachyrhizi

Leaves of pot-grown soybean seedlings were sprayed to run-off with anaqueous suspension, containing the concentration of active ingredient ortheir mixture as described below. The plants were allowed to air-dry.The trial plants were cultivated for 1 day in a greenhouse chamber at 23to 27° C. and a relative humidity between 60 and 80%. Then the plantswere inoculated with spores of Phakopsora pachyrhizi. To ensure thesuccess the artificial inoculation, the plants were transferred to ahumid chamber with a relative humidity of about 95% and 20-24° C. for 24h. The trial plants were cultivated for fourteen days in a greenhousechamber at 23 to 27° C. and a relative humidity between 60 and 80%.

In this test, the plants which had been treated with 250 ppm of theactive compound V-1, V-2, V-3, V-4, V-5, V-8, V-10, V-11, V-14, V-16,V-17, V-23, V-26, V-27, V-31, V-32, V-34, V-37, V-42, V-43, V-44, V-47or V-48 showed a diseased leaf area of at most 20%, whereas theuntreated plants showed 94% diseased leaf area.

Use Example 2: Preventative Control of Brown Rust on Wheat Caused byPuccinia Recondite

The first two developed leaves of pot-grown wheat seedling were sprayedto run-off with an aqueous suspension, containing the concentration ofactive ingredient or their mixture as described below. The next day theplants were inoculated with spores of Puccinia recondita. To ensure thesuccess the artificial inoculation, the plants were transferred to ahumid chamber without light and a relative humidity of 95 to 99% and 20to 24° C. for 24 h. Then the trial plants were cultivated for 6 days ina greenhouse chamber at 20 to 24° C. and a relative humidity between 65and 70%.

In this test, the plants which had been treated with 250 ppm of theactive compound V-1, V-2, V-4, V-5, V-7, V-10, V-11, V-14, V-15, V-25,V-26, V-27, V-35 or V-38 showed a diseased leaf area of at most 20%,whereas the untreated plants showed 86% diseased leaf area.

Use Example 3: Preventative Control of Leaf Blotch on Wheat Caused bySeptoria tritici

Leaves of pot-grown wheat seedling were sprayed to run-off with anaqueous suspension of the active compound or their mixture, prepared asdescribed. The plants were allowed to air-dry. At the following day theplants were inoculated with an aqueous spore suspension of Septoriatritici. Then the trial plants were immediately transferred to a humidchamber at 18 to 22° C. and a relative humidity close to 100%. After 4days the plants were transferred to a chamber with 18 to 22° C. and arelative humidity close to 70% and kept there for 4 weeks.

In this test, the plants which had been treated with 250 ppm of theactive compound V-1, V-2, V-3, V-4, V-5, V-6, V-7, V-9, V-11, V-12,V-13, V-14, V-15, V-16, V-26, V-27, V-29, V-30, V-31, V-32, V-33, V-36,V-37, V-39 or V-40 showed a diseased leaf area of at most 20%, whereasthe untreated plants showed 93% diseased leaf area.

Use Example 4: Control of Late Blight on Tomatoes Caused by Phytophthorainfestans

Young seedlings of tomato plants were grown in pots. These plants weresprayed to run-off with an aqueous suspension, containing theconcentration of active ingredient or their mixture mentioned in thetable below. The next day the treated plants were inoculated with anaqueous suspension of sporangia of Phytophthora infestans. Afterinoculation, the trial plants were immediately transferred to a humidchamber and kept for 6 days at 18 to 20° C. and a relative humidityclose to 100%.

In this test, the plants which had been treated with 250 ppm of theactive compound V-3, V-4, V-6, V-9, V-14, V-15, V-16, V-17, V-18, V-19,V-20, V-21, V-22, V-23, V-24, V-26, V-27, V-28, V-29, V-46 or V-47showed a diseased leaf area of at most 20%, whereas the untreated plantsshowed 80% diseased leaf area.

Use Example 5: Control of Late Blight on Tomatoes Caused by Phytophthorainfestans

Young seedlings of tomato plants were grown in pots. These plants weresprayed to run-off with an aqueous suspension, containing theconcentration of active ingredient or their mixture mentioned in thetable below. Seven days later the treated plants were inoculated with anaqueous suspension of sporangia of Phytophthora infestans. Afterinoculation, the trial plants were immediately transferred to a humidchamber and kept for 6 days at 18 to 20° C. and a relative humidityclose to 100%.

In this test, the plants which had been treated with 250 ppm of theactive compound V-4, V-15, V-17, V-23, V-28, V-41, V-45 or V-49 showed adiseased leaf area of at most 20%, whereas the untreated plants showed60% diseased leaf area.

Use Example 6: Preventative Fungicidal Control of Botiytis Cinerea onLeaves of Green Pepper

Young seedlings of green pepper were grown in pots to the 4 to 5 leafstage. These plants were sprayed to run-off with an aqueous suspension,containing the concentration of active ingredient or their mixturementioned in the table below. The next day the plants were inoculatedwith a aqueous biomalt solution containing the spore suspension ofBotrytis cinerea. Then the plants were immediately transferred to ahumid chamber and kept for 5 days at 22 to 24° C. and a relativehumidity close to 100%.

In this test, the plants which had been treated with 250 ppm of theactive compound V-2, V-4, V-12, V-13, V-15 or V-40 showed a diseasedleaf area of at most 20%, whereas the untreated plants showed 89%diseased leaf area.

1-14. (canceled)
 15. A compound of formula I

wherein: R^(a2), R^(a5) independently of each other, are hydrogen,halogen, CN, NO₂, OH, SH, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio,C₁-C₄-alkylsulfinyl, C₁-C₄-haloalkylsulfinyl, C₁-C₄-alkylsulfonyl,C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,C₁-C₄-alkoxy-C₁-C₄-alkoxy, C₂-C₄-alkenyl, C₂-C₄-alkynyl,C₂-C₄-haloalkenyl, C₂-C₄-haloalkynyl, C₃-C₈-cycloalkyl,C₃-C₈-cycloalkyloxy, C₃-C₈-cycloalkyl-C₁-C₄-alkyl, NR^(A)R^(B), C(═O)R¹,C(═NOR″)R′″ or —C(═NH)—O—R′″; R^(A),R^(B) independently of each otherare hydrogen, C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, phenyl, benzyl,C₃-C₈-cycloalkyl, C₃-C₈-cycloalkenyl or —(C═O)—R′; R′ is hydrogen, OH,NH₂, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl,C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylamino ordi(C₁-C₄-alkyl)amino; R″ is hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₂-C₄-alkenyl, C₂-C₄-alkynyl or C₁-C₄-alkoxy-C₁-C₄-alkyl, R′″ ishydrogen or C₁-C₄-alkyl; R^(ab) is halogen; R is hydrogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl,C₂-C₄-haloalkenyl, C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, CN, CH₂CN,NR^(A)R^(B) or CH₂—O—C(═O)R¹; R¹, R² independently of each other arehydrogen, halogen, CN, OH, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl,C₁-C₄-haloalkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl,C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, C₃-C₈-cycloalkyl,C₃-C₈-cycloalkyl-C₁-C₄-alkyl, C₃-C₈-cycloalkyloxy, NR^(A)R^(B), C(═O)R,C(═NOR″)R′″, —C(═NH)—O—R″ or benzyl wherein the phenyl moiety of benzylis unsubstituted or carries 1, 2, 3, 4, or 5 substituents selected fromthe group consisting of CN, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, (C₁-C₄-alkoxy)carbonyl anddi(C₁-C₄-alkyl)aminocarbonyl, or two radicals R¹ and R² that are boundto the same carbon atom form together with said carbon atom a saturatedor partially unsaturated 3-, 4-, 5-, 6-, or 7-membered carbocycle or asaturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-memberedheterocycle, wherein the ring member atoms of the abovementionedheterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatomsselected from the group of N, O and S, and wherein the abovementionedcycle is unsubstituted or carries 1, 2, 3 or 4 substituents selectedfrom halogen, CN, OH, SH, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio;and one or two CH₂ groups of the abovementioned cycles may berespectively replaced by one or two C═O or C═S groups; X is a divalentgroup selected from —CR³R⁴—, —C(═NR^(D))— and —C(═NOR^(D))—, whereinR^(D) is hydrogen or C₁-C₄-alkyl, and wherein R³ and R⁴ independently ofeach other are hydrogen, CN, C₁-C₄-hydroxyalkyl, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl,C₂-C₄-haloalkenyl, C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, C₃-C₈-cycloalkyl,C₃-C₈-cycloalkyl-C₁-C₄-alkyl, C₃-C₈-cycloalkyloxy, NR^(A)R^(B), C(═O)R′,C(═NOR″)R′″, —C(═NH)—O—R′″ or benzyl wherein the phenyl moiety of benzylis unsubstituted or carries 1, 2, 3, 4, or 5 substituents selected fromthe group consisting of CN, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, (C₁-C₄-alkoxy)carbonyl anddi(C₁-C₄alkyl)aminocarbonyl, or two radicals R³ and R⁴ that are bound tothe same carbon atom form together with said carbon atom a saturated orpartially unsaturated 3-, 4-, 5-, 6-, or 7-membered carbocycle or asaturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-memberedheterocycle, wherein the ring member atoms of the abovementionedheterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatomsselected from the group of N, O and S, and wherein the abovementionedcycle is unsubstituted or carries 1, 2, 3 or 4 substituents selectedfrom halogen, CN, OH, SH, C₁-C₄-alkoxy or C₁-C₄-alkylthio; and one ortwo CH₂ groups of the abovementioned cycles may be respectively replacedby one or two C(═O) or C(═S) groups; n indicates the number ofsubstituents R^(b) on the phenyl ring and n is 0, 1, 2, 3 or 4; R^(b) ishalogen, CN, NO₂, C₁-C₄ alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄ haloalkoxy, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyl,C₂-C₄-haloalkynyl, NR^(A)R^(B), C(═NOR″)R′″ or —C(═NH)—O—R′″, it beingpossible for n=2, 3 or 4 that R^(b) are identical or different; Het is a5- or 6-membered heteroaryl, wherein the ring member atoms of theheteroaryl include besides carbon atoms 1, 2, 3 or 4 heteroatomsselected from the group of N, O and S and wherein the heteroaryl isunsubstituted or carries 1, 2, 3 or 4 identical or different groupsR^(c): R^(c) is halogen, CN, NO₂, NH₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylamino, di(C₁-C₆-alkyl)amino,C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₁-C₆-alkylsulfinyl,C₁-C₆-haloalkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl,C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-haloalkoxy-C₁-C₄-alkyl, C₂-C₆-alkenyl,C₂-C₆-alkynyl, C(═O)R′, C(═NOR″)R′″, C₃-C₈-cycloalkyl,C₃-C₈-cycloalkyl-C₁-C₄-alkyl, phenyl, phenoxy, phenoxy-C₁-C₄-alkyl or a5- or 6-membered heteroaryl, wherein the ring member atoms of theheteroaryl include besides carbon atoms 1, 2, 3 or 4 heteroatomsselected from the group of N, O and S, and wherein the aforementionedcyclic radicals are unsubstituted or carry 1, 2, 3 or 4 identical ordifferent substituents R^(d): R^(d) is halogen, CN, C₁-C₄-alkyl,C₁-C₄-alkoxy or C₁-C₄-haloalkoxy; or two radicals R^(c) that are boundto adjacent ring member atoms of the Het group form together with saidring member atoms a fused 5-, 6- or 7-membered saturated, partiallyunsaturated or aromatic carbocycle or heterocycle, wherein the ringmember atoms of the fused heterocycle include besides carbon atoms 1, 2,3 or 4 heteroatoms selected from the group of N, O and S, and whereinthe fused carbocycle or heterocycle is unsubstituted or carries 1, 2, 3or 4 identical or different radicals groups R^(e): R^(e) is halogen, CN,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy; or anN-oxide or an agriculturally acceptable salt of the compounds of formulaI.
 16. The compound according to claim 15, wherein R^(a2) and R^(a5)independently of each other are halogen, CN, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkoxy or(C₁-C₄-alkoxy)-carbonyl, and it being possible that one of both, R^(a2)or R^(a5) can in addition be hydrogen.
 17. The compound according toclaim 15, wherein R^(a6) is chlorine or fluorine.
 18. The compoundaccording to claim 15, wherein X is —CH₂—.
 19. The compound according toclaim 15, wherein R¹ and R² are both hydrogen.
 20. The compoundaccording to claim 15, wherein Het is selected from the group consistingof pyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl,pyridin-3-yl, thiazol-2-yl, pyrazin-2-yl, pyridazin-3-yl,1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl.
 21. The compound accordingto claim 15, wherein Het carries 1 or 2 radicals R^(C) which areselected from F, Cl, Br, CN, C₁-C₂-alkylsulfonyl, C₁-C₂-alkoxycarbonyl,aminocarbonyl, C₁-C₂-alkylaminocarbonyl, di(C₁-C₂-alkyl)aminocarbonyl,C₁-C₂-alkoxy, CF₃, CHF₂, OCF₃ and OCHF₂.
 22. The compound according toclaim 15, wherein R is hydrogen.
 23. A process for preparing thecompound of claim 15, wherein X is —CR³R⁴—, which comprises reacting acompound of formula II

wherein R^(a2), R^(a5) and R^(a6) are as defined in claim 15, Hal isfluorine, chlorine or bromine, with a compound of formula III

wherein R, R¹, R², R^(b), n and Het are as defined in claim 15 and X is—CR³R⁴— as defined in claim 15 in the presence of a base or a catalystor a combination of a base and a catalyst in a solvent.
 24. Anagrochemical composition which comprises an auxiliary and at least onecompound of claim
 15. 25. The agrochemical composition according toclaim 24 comprising at least one further active substance.
 26. A methodfor combating phytopathogenic harmful fungi, which process comprisestreating the fungi or the materials, plants, the soil or seeds to beprotected against fungal attack, with an effective amount of at leastone compound of claim
 15. 27. Seed treated with a compound of claim 15,in an amount of from 0.1 g to 10 kg per 100 kg of seed.
 28. The methodof claim 26, wherein, in the compound of formula I, R^(a2) and R^(a5)independently of each other are halogen, CN, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkoxy or(C₁-C₄-alkoxy)-carbonyl, and it being possible that one of both, R^(a2)or R^(a5) can in addition be hydrogen.
 29. The method of claim 26,wherein, in the compound of formula I, R^(a6) is chlorine or fluorine.30. The method of claim 26, wherein, in the compound of formula I, X is—CH₂—.
 31. The method of claim 26, wherein, in the compound of formulaI, R¹ and R² are both hydrogen.
 32. The method of claim 26, wherein, inthe compound of formula I, Het is selected from the group consisting ofpyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridine-2-yl,pyridin-3-yl, thiazol-2-yl, pyrazin-2-yl, pyridazin-3-yl,1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl.
 33. The method of claim 26,wherein, in the compound of formula I, Het carries 1 or 2 radicals R^(c)which are selected from F, Cl, Br, CN, C₁-C₂-alkylsulfonyl,C₁-C₂-alkoxycarbonyl, aminocarbonyl, C₁-C₂-alkylaminocarbonyl,di(C₁-C₂-alkyl)aminocarbonyl, C₁-C₂-alkoxy, CF₃, CHF₂, OCF₃ and OCHF₂.34. The method of claim 26, wherein, in the compound of formula I, R ishydrogen.